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| 1st(1st leg) | CD Estepona (old) | - | Real Burgos | 0:1 | ||
| 2nd (2nd leg) | Real Burgos | - | CD Estepona (old) | 3:0 | ||
| 1st(1st leg): 09/10/1991 | 2nd (2nd leg): 16/10/1991 | Winner: Real Burgos | ||||
| 1st(1st leg) | Real Valladolid | - | Valencia CF | 0:1 | ||
| 2nd (2nd leg) | Valencia CF | - | Real Valladolid | 1:1 | ||
| 1st(1st leg): 13/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Valencia CF | ||||
| 1st(1st leg) | CD Lugo | - | SD Compostela | 1:1 | ||
| 2nd (2nd leg) | SD Compostela | - | CD Lugo | 4:0 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: SD Compostela | ||||
| 1st(1st leg) | CD Málaga | - | Rayo Vallecano | 2:0 | ||
| 2nd (2nd leg) | Rayo Vallecano | - | CD Málaga | 0:0 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: CD Málaga | ||||
| 1st(1st leg) | RCD Mallorca | - | Deportivo La Coruña | 0:0 | ||
| 2nd (2nd leg) | Deportivo La Coruña | - | RCD Mallorca | 3:1 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Deportivo La Coruña | ||||
| 1st(1st leg) | Benidorm CD | - | UE Lleida | 1:1 | ||
| 2nd (2nd leg) | UE Lleida | - | Benidorm CD | 2:3 pso | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Benidorm CD | ||||
| 1st(1st leg) | Caudal Deportivo | - | Real Avilés | 2:3 | ||
| 2nd (2nd leg) | Real Avilés | - | Caudal Deportivo | 2:1 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Real Avilés | ||||
| 1st(1st leg) | Orihuela Deportiva CF | - | CD Logroñés | 2:0 | ||
| 2nd (2nd leg) | CD Logroñés | - | Orihuela Deportiva CF | 4:2 pso | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: CD Logroñés | ||||
| 1st(1st leg) | Racing Santander | - | Real Sociedad | 0:0 | ||
| 2nd (2nd leg) | Real Sociedad | - | Racing Santander | 2:1 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Real Sociedad | ||||
| 1st(1st leg) | AEC Manlleu | - | Real Zaragoza | 0:0 | ||
| 2nd (2nd leg) | Real Zaragoza | - | AEC Manlleu | 2:0 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Real Zaragoza | ||||
| 1st(1st leg) | Atlético Marbella | - | Real Betis | 0:0 | ||
| 2nd (2nd leg) | Real Betis | - | Atlético Marbella | 2:0 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Real Betis | ||||
| 1st(1st leg) | Real Murcia | - | UE Figueres | 1:0 | ||
| 2nd (2nd leg) | UE Figueres | - | Real Murcia | 2:3 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Real Murcia | ||||
| 1st(1st leg) | CE Sabadell | - | CD Tenerife | 3:1 | ||
| 2nd (2nd leg) | CD Tenerife | - | CE Sabadell | 5:0 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: CD Tenerife | ||||
| 1st(1st leg) | SD Eibar | - | Espanyol Barcelona | 2:2 | ||
| 2nd (2nd leg) | Espanyol Barcelona | - | SD Eibar | 2:0 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Espanyol Barcelona | ||||
| 1st(1st leg) | Palamós CF | - | UD Las Palmas | 3:0 | ||
| 2nd (2nd leg) | UD Las Palmas | - | Palamós CF | 0:2 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Palamós CF | ||||
| 1st(1st leg) | Tomelloso CF | - | CP Mérida | 1:1 | ||
| 2nd (2nd leg) | CP Mérida | - | Tomelloso CF | 1:0 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: CP Mérida | ||||
| 1st(1st leg) | Cartagena FC | - | Athletic Bilbao | 0:1 | ||
| 2nd (2nd leg) | Athletic Bilbao | - | Cartagena FC | 4:1 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Athletic Bilbao | ||||
| 1st(1st leg) | CF Gimnástico Alcázar | - | CD Castellón | 1:1 | ||
| 2nd (2nd leg) | CD Castellón | - | CF Gimnástico Alcázar | 2:0 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: CD Castellón | ||||
| 1st(1st leg) | Getafe CF | - | Sestao SC | 3:1 | ||
| 2nd (2nd leg) | Sestao SC | - | Getafe CF | 2:1 | ||
| 1st(1st leg): 16/10/1991 | 2nd (2nd leg): 30/10/1991 | Winner: Getafe CF | ||||
