| 3. Round | 02/10/2020 | 1. FC Union Berlin | - | 1. FSV Mainz 05 | 4:0 | ||||
| 4. Round | 18/10/2020 | FC Schalke 04 | - | 1. FC Union Berlin | 1:1 | ||||
| 5. Round | 24/10/2020 | 1. FC Union Berlin | - | SC Freiburg | 1:1 | ||||
| 7. Round | 07/11/2020 | 1. FC Union Berlin | - | Arminia Bielefeld | 5:0 |  |
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| 11. Round | 12/12/2020 | 1. FC Union Berlin | - | Bayern München | 1:1 | ||||
| 13. Round | 18/12/2020 | 1. FC Union Berlin | - | Borussia Dortmund | 2:1 | ||||
| 17. Round | 20/01/2021 | RB Leipzig | - | 1. FC Union Berlin | 1:0 | ||||
| 20. Round | 06/02/2021 | 1. FSV Mainz 05 | - | 1. FC Union Berlin | 1:0 | ||||
| 22. Round | 20/02/2021 | SC Freiburg | - | 1. FC Union Berlin | 0:1 | ||||
| 24. Round | 07/03/2021 | Arminia Bielefeld | - | 1. FC Union Berlin | 0:0 | ||||
| 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 | ||||
| 28. Round | 10/04/2021 | Bayern München | - | 1. FC Union Berlin | 1:1 | ||||
| 30. Round | 21/04/2021 | Borussia Dortmund | - | 1. FC Union Berlin | 2:0 | ||||
| 32. Round | 08/05/2021 | VfL Wolfsburg | - | 1. FC Union Berlin | 3:0 | ||||
| 34. Round | 22/05/2021 | 1. FC Union Berlin | - | RB Leipzig | 2:1 |
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