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| 1st(1st leg) | Cádiz CF | - | Athletic Club | 1:0 | ||
| 2nd (2nd leg) | Athletic Club | - | Cádiz CF | 1:2 | ||
| 1st(1st leg): 09/01/1991 | 2nd (2nd leg): 23/01/1991 | Winner: Cádiz CF | ||||
| 1st(1st leg) | Deportivo La Coruña | - | CD Málaga | 3:2 | ||
| 2nd (2nd leg) | CD Málaga | - | Deportivo La Coruña | 0:0 | ||
| 1st(1st leg): 09/01/1991 | 2nd (2nd leg): 23/01/1991 | Winner: Deportivo La Coruña | ||||
| 1st(1st leg) | Elche CF | - | Palamós CF | 2:0 | ||
| 2nd (2nd leg) | Palamós CF | - | Elche CF | 0:0 | ||
| 1st(1st leg): 09/01/1991 | 2nd (2nd leg): 23/01/1991 | Winner: Elche CF | ||||
| 1st(1st leg) | UD Las Palmas | - | RC Celta | 2:0 | ||
| 2nd (2nd leg) | RC Celta | - | UD Las Palmas | 1:2 | ||
| 1st(1st leg): 09/01/1991 | 2nd (2nd leg): 23/01/1991 | Winner: UD Las Palmas | ||||
| 1st(1st leg) | Real Murcia | - | CD Logroñés | 1:0 | ||
| 2nd (2nd leg) | CD Logroñés | - | Real Murcia | 3:0 | ||
| 1st(1st leg): 09/01/1991 | 2nd (2nd leg): 23/01/1991 | Winner: CD Logroñés | ||||
| 1st(1st leg) | Orihuela Deportiva CF | - | Espanyol Barcelona | 0:0 | ||
| 2nd (2nd leg) | Espanyol Barcelona | - | Orihuela Deportiva CF | 3:2 | ||
| 1st(1st leg): 09/01/1991 | 2nd (2nd leg): 23/01/1991 | Winner: Espanyol Barcelona | ||||
| 1st(1st leg) | Real Oviedo | - | RCD Mallorca | 1:1 | ||
| 2nd (2nd leg) | RCD Mallorca | - | Real Oviedo | 2:0 | ||
| 1st(1st leg): 09/01/1991 | 2nd (2nd leg): 23/01/1991 | Winner: RCD Mallorca | ||||
| 1st(1st leg) | Rayo Vallecano | - | Real Betis | 0:0 | ||
| 2nd (2nd leg) | Real Betis | - | Rayo Vallecano | 2:0 | ||
| 1st(1st leg): 09/01/1991 | 2nd (2nd leg): 23/01/1991 | Winner: Real Betis | ||||
| 1st(1st leg) | Real Valladolid | - | CD Tenerife | 1:0 | ||
| 2nd (2nd leg) | CD Tenerife | - | Real Valladolid | 0:1 | ||
| 1st(1st leg): 09/01/1991 | 2nd (2nd leg): 23/01/1991 | Winner: Real Valladolid | ||||
| 1st(1st leg) | Real Zaragoza | - | Sporting Gijón | 1:1 | ||
| 2nd (2nd leg) | Sporting Gijón | - | Real Zaragoza | 1:0 | ||
| 1st(1st leg): 09/01/1991 | 2nd (2nd leg): 23/01/1991 | Winner: Sporting Gijón | ||||
