| 17. Round | 25/01/2023 | 1. FSV Mainz 05 | - | Borussia Dortmund | 1:2 | ||||
| 18. Round | 28/01/2023 | 1. FSV Mainz 05 | - | VfL Bochum | 5:2 | ||||
| 19. Round | 04/02/2023 | 1. FC Union Berlin | - | 1. FSV Mainz 05 | 2:1 |  |
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| 20. Round | 11/02/2023 | 1. FSV Mainz 05 | - | FC Augsburg | 3:1 | ||||
| 21. Round | 19/02/2023 | Bayer Leverkusen | - | 1. FSV Mainz 05 | 2:3 | ||||
| 22. Round | 24/02/2023 | 1. FSV Mainz 05 | - | Bor. Mönchengladbach | 4:0 |  |
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| 23. Round | 04/03/2023 | 1. FSV Mainz 05 | - | 1899 Hoffenheim | 1:0 | ||||
| 24. Round | 11/03/2023 | Hertha BSC | - | 1. FSV Mainz 05 | 1:1 | |
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| 25. Round | 19/03/2023 | 1. FSV Mainz 05 | - | SC Freiburg | 1:1 | |
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| 26. Round | 01/04/2023 | RB Leipzig | - | 1. FSV Mainz 05 | 0:3 | |
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| 27. Round | 08/04/2023 | 1. FSV Mainz 05 | - | Werder Bremen | 2:2 | |
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| 28. Round | 15/04/2023 | 1. FC Köln | - | 1. FSV Mainz 05 | 1:1 | |
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| 29. Round | 22/04/2023 | 1. FSV Mainz 05 | - | Bayern München | 3:1 | |
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| 30. Round | 30/04/2023 | VfL Wolfsburg | - | 1. FSV Mainz 05 | 3:0 | ||||
| 31. Round | 05/05/2023 | 1. FSV Mainz 05 | - | FC Schalke 04 | 2:3 | |
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| 32. Round | 13/05/2023 | Eintracht Frankfurt | - | 1. FSV Mainz 05 | 3:0 | ||||
| 33. Round | 21/05/2023 | 1. FSV Mainz 05 | - | VfB Stuttgart | 1:4 | |
Réunion