| 1. Round | 28/08/2021 | Real Unión | - | Inter de Madrid | 2:1 |  |
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| 2. Round | 05/09/2021 | Real Valladolid B | - | Real Unión | 0:2 | |
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| 3. Round | 10/09/2021 | Real Unión | - | RC Celta B | 1:4 | ||||
| 4. Round | 19/09/2021 | UD Logroñés | - | Real Unión | 1:0 | ||||
| 5. Round | 25/09/2021 | Real Unión | - | CD Badajoz | 1:2 | ||||
| 6. Round | 03/10/2021 | Rayo Majadahonda | - | Real Unión | 1:0 | ||||
| 7. Round | 09/10/2021 | Real Unión | - | Deportivo La Coruña | 2:1 | ||||
| 8. Round | 15/10/2021 | CD Calahorra | - | Real Unión | 2:4 | ||||
| 10. Round | 31/10/2021 | Real Unión | - | Racing Santander | 1:2 | |
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| 13. Round | 21/11/2021 | SD Logroñés | - | Real Unión | 0:2 | ||||
| 17. Round | 19/12/2021 | CF Talavera | - | Real Unión | 1:3 | ||||
| 24. Round | 19/02/2022 | Real Unión | - | SD Logroñés | 2:1 | ||||
| 25. Round | 27/02/2022 | Racing Santander | - | Real Unión | 4:1 | ||||
| 21. Round | 02/03/2022 | Real Unión | - | Real Valladolid B | 2:1 | |
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| 26. Round | 06/03/2022 | Real Unión | - | CD Calahorra | 0:2 | |
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| 31. Round | 10/04/2022 | Zamora CF | - | Real Unión | 0:1 | ||||
| 35. Round | 08/05/2022 | Inter de Madrid | - | Real Unión | 2:0 | ||||
| 36. Round | 14/05/2022 | Real Unión | - | CF Talavera | 3:1 | ||||
| 38. Round | 28/05/2022 | Real Unión | - | CD Tudelano | 3:1 |
Spain