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| U | UE Llagostera | - | Valencia CF | 0:2 (0:1) | ||
| R | Valencia CF | - | UE Llagostera | 3:1 (1:0) | ||
| U: 30.10.2012 20:00 | R: 28.11.2012 19:30 | Winnaars: Valencia CF | ||||
| U | Deportivo Alavés | - | FC Barcelona | 0:3 (0:1) | ||
| R | FC Barcelona | - | Deportivo Alavés | 3:1 (1:1) | ||
| U: 30.10.2012 22:00 | R: 28.11.2012 21:30 | Winnaars: FC Barcelona | ||||
| U | CP Cacereño | - | Málaga CF | 3:4 (2:2) | ||
| R | Málaga CF | - | CP Cacereño | 0:1 (0:1) | ||
| U: 31.10.2012 20:00 | R: 27.11.2012 21:30 | Winnaars: Málaga CF | ||||
| U | Real Jaén | - | Atlético Madrid | 0:3 (0:1) | ||
| R | Atlético Madrid | - | Real Jaén | 1:0 (1:0) | ||
| U: 31.10.2012 20:00 | R: 28.11.2012 19:30 | Winnaars: Atlético Madrid | ||||
| U | UD Almería | - | Celta de Vigo | 2:0 (0:0) | ||
| R | Celta de Vigo | - | UD Almería | 3:0 (0:0, 2:0) n.v. | ||
| U: 31.10.2012 20:00 | R: 29.11.2012 19:30 | Winnaars: Celta de Vigo | ||||
| U | Real Zaragoza | - | Granada CF | 1:0 (0:0) | ||
| R | Granada CF | - | Real Zaragoza | 2:1 (1:0) | ||
| U: 31.10.2012 20:00 | R: 29.11.2012 19:30 | Winnaars: Real Zaragoza | ||||
| U | UD Las Palmas | - | Rayo Vallecano | 1:0 (1:0) | ||
| R | Rayo Vallecano | - | UD Las Palmas | 0:0 (0:0) | ||
| U: 31.10.2012 21:00 | R: 27.11.2012 19:30 | Winnaars: UD Las Palmas | ||||
| U | CD Alcoyano | - | Real Madrid | 1:4 (0:2) | ||
| R | Real Madrid | - | CD Alcoyano | 3:0 (0:0) | ||
| U: 31.10.2012 22:00 | R: 27.11.2012 21:30 | Winnaars: Real Madrid | ||||
| U | SD Eibar | - | Athletic Club | 0:0 (0:0) | ||
| R | Athletic Club | - | SD Eibar | 1:1 (0:0) | ||
| U: 01.11.2012 12:00 | R: 12.12.2012 20:00 | Winnaars: SD Eibar | ||||
| U | Real Valladolid | - | Real Betis | 1:0 (1:0) | ||
| R | Real Betis | - | Real Valladolid | 3:0 (1:0) | ||
| U: 01.11.2012 17:00 | R: 27.11.2012 19:30 | Winnaars: Real Betis | ||||
| U | UD Melilla | - | Levante UD | 1:0 (1:0) | ||
| R | Levante UD | - | UD Melilla | 4:1 (1:1) | ||
| U: 01.11.2012 18:00 | R: 28.11.2012 19:30 | Winnaars: Levante UD | ||||
| U | Sporting Gijón | - | CA Osasuna | 1:0 (1:0) | ||
| R | CA Osasuna | - | Sporting Gijón | 2:0 (0:0) | ||
| U: 01.11.2012 19:00 | R: 27.11.2012 19:30 | Winnaars: CA Osasuna | ||||
| U | Córdoba CF | - | Real Sociedad | 2:0 (1:0) | ||
| R | Real Sociedad | - | Córdoba CF | 2:2 (1:0) | ||
| U: 01.11.2012 19:00 | R: 27.11.2012 19:30 | Winnaars: Córdoba CF | ||||
| U | SD Ponferradina | - | Getafe CF | 0:4 (0:2) | ||
| R | Getafe CF | - | SD Ponferradina | 0:0 (0:0) | ||
| U: 01.11.2012 19:00 | R: 28.11.2012 19:30 | Winnaars: Getafe CF | ||||
| U | Sevilla FC | - | Espanyol | 3:1 (1:0) | ||
| R | Espanyol | - | Sevilla FC | 0:3 (0:2) | ||
| U: 01.11.2012 19:00 | R: 28.11.2012 21:30 | Winnaars: Sevilla FC | ||||
| U | Deportivo La Coruña | - | RCD Mallorca | 1:1 (0:0) | ||
| R | RCD Mallorca | - | Deportivo La Coruña | 0:0 (0:0) | ||
| U: 01.11.2012 21:00 | R: 29.11.2012 21:30 | Winnaars: RCD Mallorca | ||||
