The club sacked former boss Juan Carlos Garrido on Wednesday after the club's embarrassing Copa del Rey defeat to second division Mirandes.
Molina, 41, was previously in charge of the Yellow Submarine's second team.
The former Villarreal goalkeeper will oversee his first game on Sunday, January 8 when his side hosts Valencia in La Liga.
Restore Data
| Team | P | W | D | L | F | A | GD | PTS | |
| 1 | Atletico MadridAtletico | 18 | 12 | 5 | 1 | 33 | 12 | 21 | 41 |
| 2 | Real Madrid | 18 | 12 | 4 | 2 | 41 | 18 | 23 | 40 |
| 3 | Barcelona | 19 | 12 | 2 | 5 | 51 | 22 | 29 | 38 |
| 4 | Athletic Bilbao | 19 | 10 | 6 | 3 | 29 | 17 | 12 | 36 |
| 5 | Villarreal | 18 | 8 | 6 | 4 | 34 | 30 | 4 | 30 |
| 6 | Mallorca | 19 | 9 | 3 | 7 | 19 | 21 | -2 | 30 |
| 7 | Real Sociedad | 18 | 7 | 4 | 7 | 16 | 13 | 3 | 25 |
| 8 | GironaGirona | 18 | 7 | 4 | 7 | 26 | 25 | 1 | 25 |
| 9 | Real BetisBetis | 18 | 6 | 7 | 5 | 21 | 22 | -1 | 25 |
| 10 | Osasuna | 18 | 6 | 7 | 5 | 23 | 27 | -4 | 25 |
| 11 | Celta Vigo | 18 | 7 | 3 | 8 | 27 | 28 | -1 | 24 |
| 12 | Rayo Vallecano | 18 | 5 | 7 | 6 | 20 | 21 | -1 | 22 |
| 13 | Las PalmasLas Palmas | 18 | 6 | 4 | 8 | 23 | 27 | -4 | 22 |
| 14 | Sevilla | 18 | 6 | 4 | 8 | 20 | 27 | -7 | 22 |
| 15 | Leganes | 18 | 4 | 6 | 8 | 17 | 28 | -11 | 18 |
| 16 | AlavesAlaves | 18 | 4 | 5 | 9 | 21 | 30 | -9 | 17 |
| 17 | Getafe | 18 | 3 | 7 | 8 | 11 | 15 | -4 | 16 |
| 18 | Espanyol | 18 | 4 | 3 | 11 | 16 | 30 | -14 | 15 |
| 19 | Valencia | 17 | 2 | 6 | 9 | 16 | 26 | -10 | 12 |
| 20 | Real ValladolidValladolid | 18 | 3 | 3 | 12 | 12 | 37 | -25 | 12 |
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