| 2. Round | 26/09/2020 | Bor. Mönchengladbach | - | 1. FC Union Berlin | 1:1 |  |
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| 3. Round | 02/10/2020 | 1. FC Union Berlin | - | 1. FSV Mainz 05 | 4:0 | ||||
| 18. Round | 23/01/2021 | FC Augsburg | - | 1. FC Union Berlin | 2:1 | ||||
| 19. Round | 30/01/2021 | 1. FC Union Berlin | - | Bor. Mönchengladbach | 1:1 |  |
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| 20. Round | 06/02/2021 | 1. FSV Mainz 05 | - | 1. FC Union Berlin | 1:0 |  |
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| 22. Round | 20/02/2021 | SC Freiburg | - | 1. FC Union Berlin | 0:1 | ||||
| 23. Round | 28/02/2021 | 1. FC Union Berlin | - | 1899 Hoffenheim | 1:1 | ||||
| 25. Round | 13/03/2021 | 1. FC Union Berlin | - | 1. FC Köln | 2:1 | ||||
| 26. Round | 20/03/2021 | Eintracht Frankfurt | - | 1. FC Union Berlin | 5:2 | ||||
| 27. Round | 04/04/2021 | 1. FC Union Berlin | - | Hertha BSC | 1:1 | ||||
| 29. Round | 17/04/2021 | 1. FC Union Berlin | - | VfB Stuttgart | 2:1 | ||||
| 30. Round | 21/04/2021 | Borussia Dortmund | - | 1. FC Union Berlin | 2:0 | ||||
| 31. Round | 24/04/2021 | 1. FC Union Berlin | - | Werder Bremen | 3:1 | ||||
| 32. Round | 08/05/2021 | VfL Wolfsburg | - | 1. FC Union Berlin | 3:0 | ||||
| 33. Round | 15/05/2021 | Bayer Leverkusen | - | 1. FC Union Berlin | 1:1 | ||||
| 34. Round | 22/05/2021 | 1. FC Union Berlin | - | RB Leipzig | 2:1 | |
Germany