| 15/08/2021 | 20:00 | FC Barcelona | 4 | 2 | Real Sociedad de Fútbol |
| 21/08/2021 | 22:00 | Athletic Club | 1 | 1 | FC Barcelona |
| 29/08/2021 | 17:00 | FC Barcelona | 2 | 1 | Getafe CF |
| 11/09/2021 | 21:00 | Sevilla FC | FC Barcelona | ||
| 14/09/2021 | 21:00 | FC Barcelona | 0 | 3 | FC Bayern München |
| 20/09/2021 | 21:00 | FC Barcelona | 1 | 1 | Granada CF |
| 23/09/2021 | 22:00 | Cádiz CF | FC Barcelona | ||
| 26/09/2021 | 16:15 | FC Barcelona | Levante UD | ||
| 29/09/2021 | 21:00 | Sport Lisboa e Benfica | FC Barcelona | ||
| 02/10/2021 | 21:00 | Club Atlético de Madrid | FC Barcelona | ||
| 17/10/2021 | 20:00 | FC Barcelona | Valencia CF | ||
| 20/10/2021 | 18:45 | FC Barcelona | FK Dynamo Kyiv | ||
| 24/10/2021 | 20:00 | FC Barcelona | Real Madrid CF | ||
| 27/10/2021 | 20:00 | Rayo Vallecano de Madrid | FC Barcelona | ||
| 31/10/2021 | 21:00 | FC Barcelona | Deportivo Alavés | ||
| 02/11/2021 | 22:00 | FK Dynamo Kyiv | FC Barcelona | ||
| 07/11/2021 | 21:00 | RC Celta de Vigo | FC Barcelona | ||
| 21/11/2021 | 21:00 | FC Barcelona | RCD Espanyol de Barcelona | ||
| 23/11/2021 | 22:00 | FC Barcelona | Sport Lisboa e Benfica | ||
| 28/11/2021 | 21:00 | Villarreal CF | FC Barcelona | ||
| 05/12/2021 | 21:00 | FC Barcelona | Real Betis Balompié | ||
| 08/12/2021 | 22:00 | FC Bayern München | FC Barcelona | ||
| 12/12/2021 | 21:00 | CA Osasuna | FC Barcelona | ||
| 19/12/2021 | 21:00 | FC Barcelona | Elche CF | ||
| 02/01/2022 | 21:00 | RCD Mallorca | FC Barcelona | ||
| 09/01/2022 | 21:00 | Granada CF | FC Barcelona | ||
| 19/01/2022 | 21:00 | FC Barcelona | Rayo Vallecano de Madrid | ||
| 23/01/2022 | 21:00 | Deportivo Alavés | FC Barcelona | ||
| 06/02/2022 | 21:00 | FC Barcelona | Club Atlético de Madrid | ||
| 13/02/2022 | 21:00 | RCD Espanyol de Barcelona | FC Barcelona | ||
| 20/02/2022 | 21:00 | Valencia CF | FC Barcelona | ||
| 27/02/2022 | 21:00 | FC Barcelona | Athletic Club | ||
| 06/03/2022 | 21:00 | Elche CF | FC Barcelona | ||
| 13/03/2022 | 21:00 | FC Barcelona | CA Osasuna | ||
| 20/03/2022 | 21:00 | Real Madrid CF | FC Barcelona | ||
| 03/04/2022 | 20:00 | FC Barcelona | Sevilla FC | ||
| 10/04/2022 | 20:00 | Levante UD | FC Barcelona | ||
| 17/04/2022 | 20:00 | FC Barcelona | Cádiz CF | ||
| 20/04/2022 | 20:00 | Real Sociedad de Fútbol | FC Barcelona | ||
| 01/05/2022 | 20:00 | FC Barcelona | RCD Mallorca | ||
| 08/05/2022 | 20:00 | Real Betis Balompié | FC Barcelona | ||
| 11/05/2022 | 20:00 | FC Barcelona | RC Celta de Vigo | ||
| 15/05/2022 | 20:00 | Getafe CF | FC Barcelona | ||
| 22/05/2022 | 20:00 | FC Barcelona | Villarreal CF |