| Tamira Paszek (OOS) | Viktoria Azarenka (WRU-1) | 3-3 (Opg) |
| Carla Suarez (SPA) | Sabine Lisicki (DUI-15) | 3-6, 6-3, 6-4 |
| Marion Bartoli (FRA-9) | Shuai Peng (CHN) | 6-1, 6-3 |
| Petra Kvitova (TSJ-5) | Ksenia Pervak (KAZ) | 4-6, 7-6 (7/0), 6-0 |
| Christina McHale (USA) | Galina Voskobojeva (KAZ-LL) | 7-5, 3-6, 6-2 |
| Aleksandra Wozniak (CAN-WC) | Jelena Jankovic (SER-13) | 6-2, 6-3 |
| Varvara Lepchenko (USA) | Dominika Cibulkova (SLW-12) | 6-4, 6-4 |
| Caroline Wozniacki (DEN-7) | Kiki Bertens (NED-Kwal) | 7-5, 6-1 |
| Angelique Kerber (DUI-6) | Jekaterina Makarova (RUS) | 6-3, 6-3 |
| Roberta Vinci (ITA) | Ana Ivanovic (SER-11) | 6-0, 6-0 |
| Lucie Safarova (TSJ-16) | Sesil Karatantsjeva (KAZ-Kwal) | 6-4, 6-4 |
| Samantha Stosur (AUS-4) | Simona Halep (ROE) | 7-5, 4-4 (Opg) |
| Sara Errani (ITA-8) | Jana Cepelova (SLW-Kwal) | 6-3, 6-2 |
| Li Na (CHN-10) | Eugenie Bouchard (CAN-WC) | 6-4, 6-4 |
| Chanelle Scheepers (ZAF) | Flavia Pennetta (ITA-14) | 1-4 (Opg) |
| Agnieszka Radwanska (POL-2) | Mona Barthel (DUI) | 4-6, 6-3, 7-6 (7/5) |