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| 1st(1st leg) | Deportivo La Coruña | - | Valencia CF | 2:3 (0:2) | ||
| 2nd (2nd leg) | Valencia CF | - | Deportivo La Coruña | 4:0 (1:0) | ||
| 1st(1st leg): 06/02/1991 | 2nd (2nd leg): 27/02/1991 | Winner: Valencia CF | ||||
| 1st(1st leg) | Espanyol Barcelona | - | Real Valladolid | 2:1 (2:0) | ||
| 2nd (2nd leg) | Real Valladolid | - | Espanyol Barcelona | 2:0 (1:0) | ||
| 1st(1st leg): 06/02/1991 | 2nd (2nd leg): 27/02/1991 | Winner: Real Valladolid | ||||
| 1st(1st leg) | UD Las Palmas | - | FC Barcelona | 1:0 (0:0) | ||
| 2nd (2nd leg) | FC Barcelona | - | UD Las Palmas | 6:0 (4:0) | ||
| 1st(1st leg): 06/02/1991 | 2nd (2nd leg): 27/02/1991 | Winner: FC Barcelona | ||||
| 1st(1st leg) | Real Sociedad | - | Sporting Gijón | 1:1 (1:0) | ||
| 2nd (2nd leg) | Sporting Gijón | - | Real Sociedad | 1:0 (0:0) | ||
| 1st(1st leg): 06/02/1991 | 2nd (2nd leg): 27/02/1991 | Winner: Sporting Gijón | ||||
| 1st(1st leg) | Sevilla FC | - | Cádiz CF | 3:0 (1:0) | ||
| 2nd (2nd leg) | Cádiz CF | - | Sevilla FC | 0:3 (0:1) | ||
| 1st(1st leg): 06/02/1991 | 2nd (2nd leg): 27/02/1991 | Winner: Sevilla FC | ||||
| 1st(1st leg) | CD Logroñés | - | Real Betis | 0:0 (0:0) | ||
| 2nd (2nd leg) | Real Betis | - | CD Logroñés | 0:2 (0:1) | ||
| 1st(1st leg): 06/02/1991 | 2nd (2nd leg): 27/02/1991 | Winner: CD Logroñés | ||||
| 1st(1st leg) | Real Madrid | - | Atlético Madrid | 1:1 (0:1) | ||
| 2nd (2nd leg) | Atlético Madrid | - | Real Madrid | 1:0 (0:0) | ||
| 1st(1st leg): 07/02/1991 | 2nd (2nd leg): 27/02/1991 | Winner: Atlético Madrid | ||||
| 1st(1st leg) | Elche CF | - | RCD Mallorca | 2:1 (2:0) | ||
| 2nd (2nd leg) | RCD Mallorca | - | Elche CF | 3:1 (1:0, 2:1) aet | ||
| 1st(1st leg): 17/02/1991 | 2nd (2nd leg): 27/02/1991 | Winner: RCD Mallorca | ||||
