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| 1st(1st leg) | SD Ponferradina | - | Real Zaragoza | 1:2 | ||
| 2nd (2nd leg) | Real Zaragoza | - | SD Ponferradina | 2:2 | ||
| 1st(1st leg): 06/12/1990 | 2nd (2nd leg): 20/12/1990 | Winner: Real Zaragoza | ||||
| 1st(1st leg) | RSD Alcalá | - | Palamós CF | 2:0 | ||
| 2nd (2nd leg) | Palamós CF | - | RSD Alcalá | 3:0 | ||
| 1st(1st leg): 12/12/1990 | 2nd (2nd leg): 20/12/1990 | Winner: Palamós CF | ||||
| 1st(1st leg) | FC Andorra | - | CD Málaga | 0:1 | ||
| 2nd (2nd leg) | CD Málaga | - | FC Andorra | 5:0 | ||
| 1st(1st leg): 12/12/1990 | 2nd (2nd leg): 02/01/1991 | Winner: CD Málaga | ||||
| 1st(1st leg) | Racing Santander | - | Athletic Club | 1:3 | ||
| 2nd (2nd leg) | Athletic Club | - | Racing Santander | 2:0 | ||
| 1st(1st leg): 12/12/1990 | 2nd (2nd leg): 02/01/1991 | Winner: Athletic Club | ||||
| 1st(1st leg) | UE Sant Andreu | - | CD Logroñés | 2:2 | ||
| 2nd (2nd leg) | CD Logroñés | - | UE Sant Andreu | 1:0 | ||
| 1st(1st leg): 12/12/1990 | 2nd (2nd leg): 20/12/1990 | Winner: CD Logroñés | ||||
| 1st(1st leg) | Águilas CF | - | Rayo Vallecano | 0:2 | ||
| 2nd (2nd leg) | Rayo Vallecano | - | Águilas CF | 2:2 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 02/01/1991 | Winner: Rayo Vallecano | ||||
| 1st(1st leg) | Real Ávila CF | - | Real Oviedo | 1:2 | ||
| 2nd (2nd leg) | Real Oviedo | - | Real Ávila CF | 0:0 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 02/01/1991 | Winner: Real Oviedo | ||||
| 1st(1st leg) | CD Badajoz | - | Real Betis | 1:0 | ||
| 2nd (2nd leg) | Real Betis | - | CD Badajoz | 4:1 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 20/12/1990 | Winner: Real Betis | ||||
| 1st(1st leg) | Atlético Baleares | - | Deportivo La Coruña | 0:0 | ||
| 2nd (2nd leg) | Deportivo La Coruña | - | Atlético Baleares | 1:0 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 19/12/1990 | Winner: Deportivo La Coruña | ||||
| 1st(1st leg) | Benidorm CD | - | Real Valladolid | 1:1 | ||
| 2nd (2nd leg) | Real Valladolid | - | Benidorm CD | 7:0 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 02/01/1991 | Winner: Real Valladolid | ||||
| 1st(1st leg) | CD Castellón | - | Espanyol Barcelona | 1:1 | ||
| 2nd (2nd leg) | Espanyol Barcelona | - | CD Castellón | 2:0 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 02/01/1991 | Winner: Espanyol Barcelona | ||||
| 1st(1st leg) | SCD Durango | - | Sporting Gijón | 1:2 | ||
| 2nd (2nd leg) | Sporting Gijón | - | SCD Durango | 1:0 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 02/01/1991 | Winner: Sporting Gijón | ||||
| 1st(1st leg) | Getafe CF | - | UD Las Palmas | 1:2 | ||
| 2nd (2nd leg) | UD Las Palmas | - | Getafe CF | 2:2 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 02/01/1991 | Winner: UD Las Palmas | ||||
| 1st(1st leg) | SD Huesca | - | Cádiz CF | 0:0 | ||
| 2nd (2nd leg) | Cádiz CF | - | SD Huesca | 5:4 pso | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 20/12/1990 | Winner: Cádiz CF | ||||
| 1st(1st leg) | Real Murcia | - | Real Burgos | 3:2 | ||
| 2nd (2nd leg) | Real Burgos | - | Real Murcia | 0:2 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 20/12/1990 | Winner: Real Murcia | ||||
| 1st(1st leg) | CE Sabadell | - | RCD Mallorca | 0:3 | ||
| 2nd (2nd leg) | RCD Mallorca | - | CE Sabadell | 4:1 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 19/12/1990 | Winner: RCD Mallorca | ||||
| 1st(1st leg) | CD San Roque | - | Orihuela Deportiva CF | 0:1 | ||
| 2nd (2nd leg) | Orihuela Deportiva CF | - | CD San Roque | 1:0 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 27/12/1990 | Winner: Orihuela Deportiva CF | ||||
| 1st(1st leg) | CF Sporting Mahonés | - | Elche CF | 1:2 | ||
| 2nd (2nd leg) | Elche CF | - | CF Sporting Mahonés | 2:1 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 03/01/1991 | Winner: Elche CF | ||||
| 1st(1st leg) | CD Tenerife | - | CA Osasuna | 3:0 | ||
| 2nd (2nd leg) | CA Osasuna | - | CD Tenerife | 2:1 | ||
| 1st(1st leg): 13/12/1990 | 2nd (2nd leg): 20/12/1990 | Winner: CD Tenerife | ||||
| 1st(1st leg) | UD Salamanca | - | RC Celta | 2:2 | ||
| 2nd (2nd leg) | RC Celta | - | UD Salamanca | 1:0 | ||
| 1st(1st leg): 20/12/1990 | 2nd (2nd leg): 02/01/1991 | Winner: RC Celta | ||||
