| 1. Round | 11/08/2013 | 1. FSV Mainz 05 | - | VfB Stuttgart | 3:2 | ||||
| 2. Round | 17/08/2013 | SC Freiburg | - | 1. FSV Mainz 05 | 1:2 |  |
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| 3. Round | 24/08/2013 | 1. FSV Mainz 05 | - | VfL Wolfsburg | 2:0 | ||||
| 4. Round | 31/08/2013 | Hannover 96 | - | 1. FSV Mainz 05 | 4:1 | ||||
| 5. Round | 14/09/2013 | 1. FSV Mainz 05 | - | FC Schalke 04 | 0:1 | ||||
| 6. Round | 21/09/2013 | 1. FSV Mainz 05 | - | Bayer Leverkusen | 1:4 | ||||
| 7. Round | 28/09/2013 | Hertha BSC | - | 1. FSV Mainz 05 | 3:1 | ||||
| 8. Round | 05/10/2013 | 1. FSV Mainz 05 | - | 1899 Hoffenheim | 2:2 | ||||
| 10. Round | 26/10/2013 | 1. FSV Mainz 05 | - | Eintracht Braunschweig | 2:0 | ||||
| 11. Round | 03/11/2013 | FC Augsburg | - | 1. FSV Mainz 05 | 2:1 |
Germany