Eden Hazard's opener on 10 minutes was cancelled out by Luis Suarez, before Sandro fired the Catalans ahead in style.
However, Gary Cahill pounced in the closing minutes with a leaping header to equalise, before Loic Remy struck the winning penalty in the shootout to seal the victory.
Below, relive the drama in Maryland with our live text commentary.
There will never be anything 'friendly' about a Chelsea - Barcelona meeting, will there? Whether it's a Champions League semi-final or an International Champions Cup encounter, both sides will find a way to kick off. It's not quite Israel - Palestine level of hostility - it's worse! Okay it's not, but there's so much bad blood that it makes whatever T. Swift is singing about in her latest tune look like child's play. Which it probably is. Anywho, I'm Shane, and I'll be guiding you through all the action as both outfits look to conclude their US tour in a relatively peaceful manner. Good luck.
Popcorn? Check. Shades to enjoy the fireworks? Check. An embed of Gary Neville's famous sex noise? Check. Indeed, from Jose Mourinho accusing referees - who then had to retire due to death threats from Chelsea fans - of favouring Barcelona. To last-minute winners that settled relatively one-sided Champions League affairs in which the losing team should have had, what, six penalties? Tis' a fixture of which controversy often takes centre stage. Unfortunately.
It's also been known to throw up rather bizarre moments too. As we alluded to, remember Neville's commentary back in 2012, when Fernando Torres scored to seal Chelsea's place in the final? Me too. Unfortunately.
Anywho, before have a look at the team news why don't we look at exactly why this fixture? Okay. Long before Mourinho and Messi there was Gianluca Vialli and Patrick Kluivert. Back in 2000, Chelsea won their first leg CL quarter-final 3-1, with Luis Figo netting a priceless away goal at Stamford Bridge to give the Catalans hope. At Camp Nou, Chelsea are taught a lesson with a 5-1 defeat.
Things really got spicy five years later, when Mourinho accused referee Anders Frisk of meeting Barcelona coach Frank Rijkaard during half-time of a quarter-final first-leg that Chelsea lost 2-1 in Catalunya. However, Mourinho's men, as they so often do, managed to turn it around with a 4-2 second-leg win to reach the semi-finals. Frisk later announced his retirement after he and his family were inundated with death threats from Chelsea fans.
Four years later, Chelsea - under stand-in coach Guus Hiddink - look like beating Barcelona 1-0 on aggregate to reach the Champions League final. Michael Essien's stunning volley looked to be enough as the Blues are seconds away. But Andres Iniesta pops up with an equally fine finish in the dying seconds as the Catalans advance on away goals. There were shades of injustice, though, as the Blues had several legitimate penalty appeals waved away by Tom Henning Ovrebo.
Now that we've had a bit of a history lesson, shall we take a quick check on the team news? Why not. Is a certain Radamel Falcao going to appear in Chelsea's first XI for the first time? Time will tell. Before we get the team sheets, we should note that Lionel Messi and Neymar are not here due to their Copa America commitments earlier this month.
Right, so no Falcao, but who cares! We've still got Costa, Hazard, Oscar, Matic, Fabregas and four of the back five that helped Chelsea to the title. John Terry sits out in place of Kurt Zouma, while there is also room for young Brazilian starlet Kenedy. Isn't Washington quite close to Maryland? Historically, Kenedy's near Washington don't fare well, do they? Hopefully it will for him.
On to Barcelona now, and sadly for us, and them, Messi and Neymar are still not present as we noted. Luis Suarez is, though. He partners Sandro and Munir El Hadaddi in a three-pronged attack, with Ivan Rakitic, Sergio Busquets and Gerard 'Mix'em and Cook'em in a Pot Like' Gumbau. Straight Outta La Masia.
Given that both are champions of England and Spain respectively, would it be fair to assume that they've enjoyed red-hot pre-seasons thus far? Actually, no.
Chelsea were beaten 4-2 by New York Red Bulls last week - a Red Bulls team without virtually all of their best players - and then edged out Paris Saint-Germain on penalties a few days later following a drab 1-1 draw in regulation. Things get slightly more serious for them this weekend with a Community Shield outing with Arsenal at Wembley.
And what about Barcelona? Well Luis Enrique's men, who only went and won the treble last term, laboured to a 2-0 win over Los Angeles Galaxy in their International Champions Cup opener, before losing 3-1 to Manchester United last time out.
PREDICTION! Right, we're about 15 minutes from kickoff. Prediction? Anyone? Okay. Some say it's a futile exercise attempting to predict pre-season friendlies, and we fully intend to prove the cynics right. For the sake of fun, though, let's punt for a 2-2 draw.
Let's hope Diego Costa brought his shooting boots to Maryland. He missed a number of gilt-edged chances against NY Red Bulls last week - including TWO open goal. Consequently, he and Oscar - who also missed a few whoppers - have devised a cunning plan to get rid of the cursed footwear. Geniuses.
Yep, we're probably looking at a 01:10 am kickoff, because I can confirm that the players are still warming up. That's the scheduled time. It's worth noting that games in North America are nearly always delayed for some bizarre reason. If I was a betting man I'd say we'll get underway at about 01:16. Quote me.
Scratch that. The images I saw were pre-recorded it seems. The players are lining up in the tunnel - but we're still delayed because that suggests it was a 1am kickoff.
KICKOFF: Aaaaaaaaaaaaaaaaaand we're off at FedEx Field. Chelsea, playing in their white kit, get us underway in front of this 74,000-strong crowd. Let's go.
Bright-ish start for Barcelona, as Ivan Rakitic and Luis Suarez have the fans WOWing in the opening minutes with a couple of one-touch passes and one-twos etc. Promising.
CHANCE! Very, very nearly 1-0 to Chelsea, as ex-Barcelona man Fabregas swings a fine free kick into the box and Kurt Zouma's header is palmed away by Marc Andre Ter Stegen. Fine save.
Chelsea have another free kick here as the troublesome Eden Hazard is blocked off by Marc Bartra. More from the same from Fabregas you'd suspect. Let's see...
It's another classy delivery from the Spaniard, as Nemanja Matic heads just over. However, the flag went up moments after connecting with the header. He's a bit like The Terminator Matic, isn't he? He wandered into Stamford Bridge completely naked following a thunder storm, according to legend, and then they signed him.
What a fine goal this is, and it's from a very reliable source. Hazard picks the ball up in midfield, ghosts past a few half-hearted challenges before getting into a shooting position. From there, it's easy as the Belgian fires past Ter Stegen. Different class.
Huge challenge from Adriano. Oscar looks set to race through on goal due to Barca's defensive line being ridiculously high, but Adriano comes out of nowhere and clears the danger. Massive.
SAVE! Better from Barcelona this. The ball comes to Rakitic on the right-hand side, and the Croatian ace fires a first-time shot at goal but Courtois beats it away with ease. Lovely through ball from Suarez in the build-up.
PENALTY APPEAL! This is a cracker. Real end-to-end stuff. And Barca are slightly fortunate not to concede a penalty, as Costa capitalises on their ridiculously high defensive line again, cutting inside Mathieu before being fouled by Gerard Gumbau in the area but the referee is having none of it. There was contact. Poor decision.
Things have slowed down a little in recent minutes but there is a sense that it could explode to life again at any moment. It's that type of game. Barcelona on top at the moment.
CLOSE! What a ball this is from Adriano, who swings in a delicious cross as Suarez looks poised to head home, but it's a tiny bit too high for the Uruguayan, whose glancing header is nowhere near goal. Better from the Catalans.
OFF THE BAR! So unlucky from Oscar, whose beautiful curling effort bounces off the crossbar and Barcelona clear. For a moment there, Ter Stegen was like a statue; completely motionless.
This is kind of worrying, as Hazard lies on the ground clutching his shin following a challenge from Busquets. If I'm a Chelsea fan, I'm concerned by this because the season kicks off in less than two weeks!
SAVE! Another save from the Belgian, but this one is far easier as he beats away Sandro's effort after he cut inside on to his right boot. Barcelona on top.
CHANCE! Oh Diego Costa. It could, and definitely should, be 2-0. Barca's high defensive line undermines them again as Costa races through on goal but, with just Ter Stegen to beat, opens up his body and slots it wide! He's had a rotten pre-season thus far and it doesn't look like improving.
SAVE! Oh lord yet ANOTHER fine stop from Courtois. Suarez turns Zouma with ease before lashing a right-footed effort at goal, but the Belgian is equal to it again. What a keeper this fellow is.
CHANCE! Suarez makes a mug of Zouma yet again, sliding a fine ball across the face of goal as Rakitic looks certain to equalise, but Cahill is up like a light and puts enough pressure on the shot as Rakitic slices well, well wide. Great defending.
That's all she wrote in a brilliant first half it must be said. Chelsea lead through Eden Hazard's fantastic solo effort on the 10-minute mark. Chelsea have had more than enough chances to stretch further ahead, while Barca have had plenty too. Courtois is the reason why the Catalans are yet to score. He's had a fine game thus far, denying Suarez on a host of occasions.
SHOT! Diego Costa couldn't score in a you know what at the moment. Great build-up from the Blues, but the Spain international then tries to bend one around Mathieu and Ter Stegen, but it's high and wide.
This is a fantastic finish by Suarez, who benefits from a shocking defensive header from Azpilicueta before waiting, and then lifting a brilliant lob over Courtois from such a little distance. Kurt Zouma attempted to keep it out, but it looked to have crossed the line.
SHOT! Hmm, this is ambitious from Rakitic, who takes aim from about 30 yards but his effort flies over the bar - and probably out of the stadium truth be told.
Oh my word. What a fine finish this is. Sandro, who was not one of the eight subs made by Luis Enrique, repays his manager's patience instantly, cutting inside Ivanovic before curling past Courtois. It nestled into the top corner. Brilliant finish from the youngster.
SHOT! What an introduction this would've been, as Falcao looks to equalise with a overhead but it, well, goes high and wide. Still, that wasn't the attempt of a man lacking in confidence. It bodes well.
Courtois, who's had a fine game, is almost embarrassed here. He tries to trick Pedro but his pocket his picket, yet the angle is against him for a shot and it trickles out for a goal kick.
CHANCE! Oh my. Should be 2-2 - which is what we predicted! Falcao lays it off to Ramires, who thrashes wide of the near post with a first-time strike from close range. That's a bad, bad miss.
It's all square again. It's a shocker from Jordi Masip, who travelled well off his line to punch a corner, but Gary Cahill beats him to the ball and heads into an empty net. Masip did connect with his punch - but it struck Cahill's face! Looks like a broken nose.
Aaaaaaaaaaand penalties it is. At least we got our pre-match prediction right. Literally has never happened before I don't think. Don't go anywhere because we go to spot-kicks.
Had fun? I have. Probably the best game of the International Champions Cup thus far. Chelsea's defeat to NY Red Bulls was entertaining, but this was better.