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| 1st(1st leg) | CD Alavés | - | RC Celta | 0:0 (0:0) | ||
| 2nd (2nd leg) | RC Celta | - | CD Alavés | 0:1 (0:0) | ||
| 1st(1st leg): 24/10/2006 19:45 | 2nd (2nd leg): 09/11/2006 19:45 | Winner: CD Alavés | ||||
| 1st(1st leg) | Atlético Madrid | - | Levante UD | 0:1 (0:0) | ||
| 2nd (2nd leg) | Levante UD | - | Atlético Madrid | 2:4 (0:0, 0:1, 0:1) pso | ||
| 1st(1st leg): 24/10/2006 20:00 | 2nd (2nd leg): 13/12/2006 20:00 | Winner: Atlético Madrid | ||||
| 1st(1st leg) | Racing Portuense | - | Valencia CF | 1:2 (1:1) | ||
| 2nd (2nd leg) | Valencia CF | - | Racing Portuense | 2:0 (2:0) | ||
| 1st(1st leg): 25/10/2006 18:00 | 2nd (2nd leg): 08/11/2006 21:00 | Winner: Valencia CF | ||||
| 1st(1st leg) | Écija Balompié | - | Real Madrid | 1:1 (0:0) | ||
| 2nd (2nd leg) | Real Madrid | - | Écija Balompié | 5:1 (0:0) | ||
| 1st(1st leg): 25/10/2006 19:00 | 2nd (2nd leg): 09/11/2006 20:00 | Winner: Real Madrid | ||||
| 1st(1st leg) | Peña Sport FC | - | CA Osasuna | 0:0 (0:0) | ||
| 2nd (2nd leg) | CA Osasuna | - | Peña Sport FC | 4:0 (1:0) | ||
| 1st(1st leg): 25/10/2006 19:30 | 2nd (2nd leg): 08/11/2006 20:00 | Winner: CA Osasuna | ||||
| 1st(1st leg) | Gimnástica Segoviana | - | Sevilla FC | 0:1 (0:1) | ||
| 2nd (2nd leg) | Sevilla FC | - | Gimnástica Segoviana | 3:0 (2:0) | ||
| 1st(1st leg): 25/10/2006 19:30 | 2nd (2nd leg): 08/11/2006 20:00 | Winner: Sevilla FC | ||||
| 1st(1st leg) | Deportivo La Coruña | - | Racing Santander | 1:0 (0:0) | ||
| 2nd (2nd leg) | Racing Santander | - | Deportivo La Coruña | 1:3 (1:0, 1:0, 1:0) pso | ||
| 1st(1st leg): 25/10/2006 19:45 | 2nd (2nd leg): 08/11/2006 19:45 | Winner: Deportivo La Coruña | ||||
| 1st(1st leg) | Rayo Vallecano | - | Espanyol Barcelona | 1:1 (1:0) | ||
| 2nd (2nd leg) | Espanyol Barcelona | - | Rayo Vallecano | 0:1 (0:0) | ||
| 1st(1st leg): 25/10/2006 19:45 | 2nd (2nd leg): 08/11/2006 19:45 | Winner: Rayo Vallecano | ||||
| 1st(1st leg) | Real Valladolid | - | Gimnàstic de Tarragona | 1:0 (0:0) | ||
| 2nd (2nd leg) | Gimnàstic de Tarragona | - | Real Valladolid | 1:3 (1:0) | ||
| 1st(1st leg): 25/10/2006 19:45 | 2nd (2nd leg): 08/11/2006 19:30 | Winner: Real Valladolid | ||||
| 1st(1st leg) | Xerez CD | - | Getafe CF | 0:2 (0:0) | ||
| 2nd (2nd leg) | Getafe CF | - | Xerez CD | 1:2 (0:2) | ||
| 1st(1st leg): 25/10/2006 20:00 | 2nd (2nd leg): 08/11/2006 18:00 | Winner: Getafe CF | ||||
| 1st(1st leg) | Málaga CF | - | Real Sociedad | 4:1 (1:1) | ||
| 2nd (2nd leg) | Real Sociedad | - | Málaga CF | 2:1 (1:0) | ||
| 1st(1st leg): 25/10/2006 20:00 | 2nd (2nd leg): 08/11/2006 19:00 | Winner: Málaga CF | ||||
| 1st(1st leg) | Hércules CF | - | Real Zaragoza | 1:1 (1:0) | ||
| 2nd (2nd leg) | Real Zaragoza | - | Hércules CF | 2:0 (0:0) | ||
| 1st(1st leg): 25/10/2006 20:00 | 2nd (2nd leg): 08/11/2006 20:00 | Winner: Real Zaragoza | ||||
| 1st(1st leg) | Recreativo Huelva | - | Real Betis | 0:0 (0:0) | ||
| 2nd (2nd leg) | Real Betis | - | Recreativo Huelva | 2:0 (1:0) | ||
| 1st(1st leg): 25/10/2006 20:30 | 2nd (2nd leg): 08/11/2006 21:00 | Winner: Real Betis | ||||
| 1st(1st leg) | CD Castellón | - | Villarreal CF | 0:2 (0:2) | ||
| 2nd (2nd leg) | Villarreal CF | - | CD Castellón | 2:0 (1:0) | ||
| 1st(1st leg): 25/10/2006 20:30 | 2nd (2nd leg): 08/11/2006 19:00 | Winner: Villarreal CF | ||||
| 1st(1st leg) | CF Badalona | - | FC Barcelona | 1:2 (0:0) | ||
| 2nd (2nd leg) | FC Barcelona | - | CF Badalona | 4:0 (2:0) | ||
| 1st(1st leg): 25/10/2006 21:00 | 2nd (2nd leg): 08/11/2006 21:00 | Winner: FC Barcelona | ||||
| 1st(1st leg) | Athletic Bilbao | - | RCD Mallorca | 1:1 (1:0) | ||
| 2nd (2nd leg) | RCD Mallorca | - | Athletic Bilbao | 2:1 (1:0, 1:1) aet | ||
| 1st(1st leg): 25/10/2006 21:00 | 2nd (2nd leg): 08/11/2006 21:00 | Winner: RCD Mallorca | ||||
