| 2. Round | 19/08/2006 | Borussia Dortmund | - | 1. FSV Mainz 05 | 1:1 | ||||
| 3. Round | 27/08/2006 | 1. FSV Mainz 05 | - | Eintracht Frankfurt | 1:1 | ||||
| 4. Round | 16/09/2006 | Energie Cottbus | - | 1. FSV Mainz 05 | 2:0 | ||||
| 6. Round | 30/09/2006 | 1. FC Nürnberg | - | 1. FSV Mainz 05 | 1:1 | ||||
| 7. Round | 13/10/2006 | 1. FSV Mainz 05 | - | Alemannia Aachen | 1:3 | ||||
| 8. Round | 21/10/2006 | Arminia Bielefeld | - | 1. FSV Mainz 05 | 1:0 |  |
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| 9. Round | 27/10/2006 | 1. FSV Mainz 05 | - | Werder Bremen | 1:6 | ||||
| 10. Round | 04/11/2006 | Bayer Leverkusen | - | 1. FSV Mainz 05 | 1:1 | ||||
| 11. Round | 07/11/2006 | 1. FSV Mainz 05 | - | VfL Wolfsburg | 1:2 | ||||
| 12. Round | 11/11/2006 | FC Schalke 04 | - | 1. FSV Mainz 05 | 4:0 | ||||
| 13. Round | 18/11/2006 | 1. FSV Mainz 05 | - | Hamburger SV | 0:0 | ||||
| 15. Round | 01/12/2006 | 1. FSV Mainz 05 | - | VfB Stuttgart | 0:0 | ||||
| 17. Round | 16/12/2006 | 1. FSV Mainz 05 | - | Bayern München | 0:4 | ||||
| 33. Round | 12/05/2007 | 1. FSV Mainz 05 | - | Bor. Mönchengladbach | 3:0 | ||||
| 34. Round | 19/05/2007 | Bayern München | - | 1. FSV Mainz 05 | 5:2 |  |
France