| Xavier Malisse (BEL) | Yen-Hsun Lu (TAI) | 3-6, 1-0 |
| Roberto Bautista (SPA) | Carlos Berlocq (ARG) | 6-2, 6-3 |
| Evgeny Donskoy (RUS) | Robin Haase (NED) | 6-4, 7-5 |
| Nicolas Mahut (FRA-Kwal) | Andrey Kuznetsov (RUS) | 6-2, 6-4 |
| Guillermo García-López (SPA) | Daniel Brands (DUI) | 7-6 (9/7), 6-2 |
| Jan Hernych (TSJ-Kwal) | Michaël Llodra (FRA) | 6-7 (5/7), 6-4, 7-5 |
| Jérémy Chardy (FRA-5) | Marius Copil (ROE-WC) | 7-5, 6-4 |
| Stanislas Wawrinka (ZWI-2) | Paolo Lorenzi (ITA) | 6-3, 7-6 (10/8) |
| Ivan Dodig (KRO) | Milos Raonic (CAN-1WC) | 6-2, 7-6 (9/7) |
| Fabio Fognini (ITA-8) | Martin Klizan (SLW) | 6-7 (6/8), 6-2, 6-2 |
| Feliciano Lopez (SPA) | Juan Monaco (ARG-4) | 6-4, 6-4 |
| Fernando Verdasco (SPA) | Albert Ramos (SPA) | 6-4, 6-0 |
| Andreas Seppi (ITA-7) | Ryan Harrison (VS-Kwal) | 3-6, 3-2 |
| Radek Stepanek (TSJ) | Philipp Kohlschreiber (DUI-3) | 7-5, 5-3 |
| Bernard Tomic (AUS) | Julien Benneteau (FRA) | 6-2, 5-7, 7-6 (7/4) |
| Kyle Edmund (GBR-WC) | Gilles Simon (FRA-2) |
| Roberta Vinci (ITA-1) | Simona Halep (ROE) | |
| Lesia Tsurenko (OEK-LL) | Stefanie Vögele (ZWI) | 6-1, 7-6 (7/4) |
| Carla Suarez (SPA-3) | Sofia Arvidsson (ZWE) | 6-3, 6-4 |
| Tsvetana Pironkova (BUL) | Irina Begu (ROE) | 7-6 (9/7), 6-2 |
| Urszula Radwanska (POL-7) | Magdalena Rybarikova (SLW) | 4-3 (Opg) |
| Kirsten Flipkens (BEL-4) | Michaëlla Krajicek (NED-WC) | 7-6 (8/6), 7-6 (7/3) |
| Garbiñe Muguruza (SPA-Kwal) | Lauren Davis (VS) | 6-2, 6-0 |
| Dominika Cibulkova (SLW-2) | Anabel Medina G. (SPA) | 2-6, 6-4, 6-3 |
| Jamie Hampton (VS-Kwal) | Su-wei Hsieh (TAI) | 6-4, 7-6 (7/2) |
| Lucie Safarova (TSJ) | Samantha Stosur (AUS-WC) | 7-6 (7/5), 6-3 |
| Angelique Kerber (DUI-3) | Jekaterina Makarova (RUS) | |
| Laura Robson (GBR) | Caroline Wozniacki (DEN-5) | 4-4 |
| Maria Kirilenko (RUS-6) | Elena Baltacha (GBR-WC) | 4-6, 6-4, 6-3 |
| Yanina Wickmayer (BEL) | Petra Kvitova (TSJ-4) | 3-6, 6-4, 7-5 |
| Jelena Vesnina (RUS) | Heather Watson (GBR) | |
| Li Na (CHN-2WC) | Marion Bartoli (FRA) | (Walk-over) |
