| Champ: |  Bob Bryan Mike Bryan |
| Runner: |  Daniel Nestor  Nenad Zimonjić |
| Score: | 6–3, 6–4 |
See main article: 2010 Mutua Madrileña Madrid Open. Daniel Nestor and Nenad Zimonjić were the defending champions, but they lost in the final against Bob and Mike Bryan 3–6, 4–6.
All seeds receive a bye into the second round.