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| 1st(1st leg) | UE Llagostera | - | Valencia CF | 0:2 (0:1) | ||
| 2nd (2nd leg) | Valencia CF | - | UE Llagostera | 3:1 (1:0) | ||
| 1st(1st leg): 30/10/2012 19:00 | 2nd (2nd leg): 28/11/2012 18:30 | Winner: Valencia CF | ||||
| 1st(1st leg) | CD Alavés | - | FC Barcelona | 0:3 (0:1) | ||
| 2nd (2nd leg) | FC Barcelona | - | CD Alavés | 3:1 (1:1) | ||
| 1st(1st leg): 30/10/2012 21:00 | 2nd (2nd leg): 28/11/2012 20:30 | Winner: FC Barcelona | ||||
| 1st(1st leg) | CP Cacereño | - | Málaga CF | 3:4 (2:2) | ||
| 2nd (2nd leg) | Málaga CF | - | CP Cacereño | 0:1 (0:1) | ||
| 1st(1st leg): 31/10/2012 19:00 | 2nd (2nd leg): 27/11/2012 20:30 | Winner: Málaga CF | ||||
| 1st(1st leg) | Real Jaén | - | Atlético Madrid | 0:3 (0:1) | ||
| 2nd (2nd leg) | Atlético Madrid | - | Real Jaén | 1:0 (1:0) | ||
| 1st(1st leg): 31/10/2012 19:00 | 2nd (2nd leg): 28/11/2012 18:30 | Winner: Atlético Madrid | ||||
| 1st(1st leg) | UD Almería | - | RC Celta | 2:0 (0:0) | ||
| 2nd (2nd leg) | RC Celta | - | UD Almería | 3:0 (0:0, 2:0) aet | ||
| 1st(1st leg): 31/10/2012 19:00 | 2nd (2nd leg): 29/11/2012 18:30 | Winner: RC Celta | ||||
| 1st(1st leg) | Real Zaragoza | - | Granada CF | 1:0 (0:0) | ||
| 2nd (2nd leg) | Granada CF | - | Real Zaragoza | 2:1 (1:0) | ||
| 1st(1st leg): 31/10/2012 19:00 | 2nd (2nd leg): 29/11/2012 18:30 | Winner: Real Zaragoza | ||||
| 1st(1st leg) | UD Las Palmas | - | Rayo Vallecano | 1:0 (1:0) | ||
| 2nd (2nd leg) | Rayo Vallecano | - | UD Las Palmas | 0:0 (0:0) | ||
| 1st(1st leg): 31/10/2012 20:00 | 2nd (2nd leg): 27/11/2012 18:30 | Winner: UD Las Palmas | ||||
| 1st(1st leg) | CD Alcoyano | - | Real Madrid | 1:4 (0:2) | ||
| 2nd (2nd leg) | Real Madrid | - | CD Alcoyano | 3:0 (0:0) | ||
| 1st(1st leg): 31/10/2012 21:00 | 2nd (2nd leg): 27/11/2012 20:30 | Winner: Real Madrid | ||||
| 1st(1st leg) | SD Eibar | - | Athletic Bilbao | 0:0 (0:0) | ||
| 2nd (2nd leg) | Athletic Bilbao | - | SD Eibar | 1:1 (0:0) | ||
| 1st(1st leg): 01/11/2012 11:00 | 2nd (2nd leg): 12/12/2012 19:00 | Winner: SD Eibar | ||||
| 1st(1st leg) | Real Valladolid | - | Real Betis | 1:0 (1:0) | ||
| 2nd (2nd leg) | Real Betis | - | Real Valladolid | 3:0 (1:0) | ||
| 1st(1st leg): 01/11/2012 16:00 | 2nd (2nd leg): 27/11/2012 18:30 | Winner: Real Betis | ||||
| 1st(1st leg) | UD Melilla | - | Levante UD | 1:0 (1:0) | ||
| 2nd (2nd leg) | Levante UD | - | UD Melilla | 4:1 (1:1) | ||
| 1st(1st leg): 01/11/2012 17:00 | 2nd (2nd leg): 28/11/2012 18:30 | Winner: Levante UD | ||||
| 1st(1st leg) | Sporting Gijón | - | CA Osasuna | 1:0 (1:0) | ||
| 2nd (2nd leg) | CA Osasuna | - | Sporting Gijón | 2:0 (0:0) | ||
| 1st(1st leg): 01/11/2012 18:00 | 2nd (2nd leg): 27/11/2012 18:30 | Winner: CA Osasuna | ||||
| 1st(1st leg) | Córdoba CF | - | Real Sociedad | 2:0 (1:0) | ||
| 2nd (2nd leg) | Real Sociedad | - | Córdoba CF | 2:2 (1:0) | ||
| 1st(1st leg): 01/11/2012 18:00 | 2nd (2nd leg): 27/11/2012 18:30 | Winner: Córdoba CF | ||||
| 1st(1st leg) | SD Ponferradina | - | Getafe CF | 0:4 (0:2) | ||
| 2nd (2nd leg) | Getafe CF | - | SD Ponferradina | 0:0 (0:0) | ||
| 1st(1st leg): 01/11/2012 18:00 | 2nd (2nd leg): 28/11/2012 18:30 | Winner: Getafe CF | ||||
| 1st(1st leg) | Sevilla FC | - | Espanyol Barcelona | 3:1 (1:0) | ||
| 2nd (2nd leg) | Espanyol Barcelona | - | Sevilla FC | 0:3 (0:2) | ||
| 1st(1st leg): 01/11/2012 18:00 | 2nd (2nd leg): 28/11/2012 20:30 | Winner: Sevilla FC | ||||
| 1st(1st leg) | Deportivo La Coruña | - | RCD Mallorca | 1:1 (0:0) | ||
| 2nd (2nd leg) | RCD Mallorca | - | Deportivo La Coruña | 0:0 (0:0) | ||
| 1st(1st leg): 01/11/2012 20:00 | 2nd (2nd leg): 29/11/2012 20:30 | Winner: RCD Mallorca | ||||
