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| 1st(1st leg) | Ciudad Nueva Santa Cruz | - | Libertad Gran Mamoré | 1:0 | ||
| 2nd (2nd leg) | Libertad Gran Mamoré | - | Ciudad Nueva Santa Cruz | 1:1 | ||
| 1st(1st leg): 12/10/2021 18:00 | 2nd (2nd leg): 17/10/2021 21:00 | Winner: Ciudad Nueva Santa Cruz | ||||
| 1st(1st leg) | Bermejo | - | Universitario de Sucre | 1:0 | ||
| 2nd (2nd leg) | Universitario de Sucre | - | Bermejo | 4:5 pso | ||
| 1st(1st leg): 12/10/2021 20:30 | 2nd (2nd leg): 17/10/2021 20:00 | Winner: Bermejo | ||||
| 1st(1st leg) | Mojocoya | - | García Agreda | 2:2 | ||
| 2nd (2nd leg) | García Agreda | - | Mojocoya | 5:4 pso | ||
| 1st(1st leg): 12/10/2021 21:30 | 2nd (2nd leg): 17/10/2021 21:00 | Winner: García Agreda | ||||
| 1st(1st leg) | Unión Maestranza | - | San Antonio Bulo Bulo | 1:5 | ||
| 2nd (2nd leg) | San Antonio Bulo Bulo | - | Unión Maestranza | 1:0 | ||
| 1st(1st leg): 13/10/2021 17:55 | 2nd (2nd leg): 17/10/2021 20:30 | Winner: San Antonio Bulo Bulo | ||||
| 1st(1st leg) | Universitario de Vinto | - | Deportivo FATIC | 2:0 | ||
| 2nd (2nd leg) | Deportivo FATIC | - | Universitario de Vinto | 1:2 | ||
| 1st(1st leg): 13/10/2021 18:00 | 2nd (2nd leg): 16/10/2021 20:00 | Winner: Universitario de Vinto | ||||
| 1st(1st leg) | Deportivo Shalon | - | Wilstermann Cooperativas | 2:1 | ||
| 2nd (2nd leg) | Wilstermann Cooperativas | - | Deportivo Shalon | 1:1 | ||
| 1st(1st leg): 13/10/2021 20:00 | 2nd (2nd leg): 17/10/2021 20:30 | Winner: Deportivo Shalon | ||||
| 1st(1st leg) | Mariscal Sucre | - | Vaca Díez | 1:1 | ||
| 2nd (2nd leg) | Vaca Díez | - | Mariscal Sucre | 1:0 | ||
| 1st(1st leg): 14/10/2021 01:00 | 2nd (2nd leg): 17/10/2021 22:00 | Winner: Vaca Díez | ||||
| 1st(1st leg) | Rosario Central de Potosí | - | Empresa Minera Huanuni | 2:6 | ||
| 2nd (2nd leg) | Empresa Minera Huanuni | - | Rosario Central de Potosí | 4:2 pso | ||
| 1st(1st leg): 14/10/2021 20:00 | 2nd (2nd leg): 17/10/2021 20:00 | Winner: Empresa Minera Huanuni | ||||
| 1st(1st leg) | Deportivo Kivón | - | Torre Fuerte | 0:0 | ||
| 2nd (2nd leg) | Torre Fuerte | - | Deportivo Kivón | 3:1 | ||
| 1st(1st leg): 15/10/2021 00:00 | 2nd (2nd leg): 17/10/2021 18:00 | Winner: Torre Fuerte | ||||
