| Champ: |  Victoria Azarenka |
| Runner: |  Li Na |
| Score: | 6–2, 1–6, 6–3 |
| Draw: | 30 (6 / 2) |
| Seeds: | 8 |
| Before Name: | Medibank International Sydney – Women's singles |
| After Name: | Apia International Sydney – Women's singles |
| Main Name: | Sydney International |
See main article: 2012 Apia International Sydney.
Li Na was the defending champion, but lost the final against Victoria Azarenka, 6–2, 1–6, 6–3.
The top two seeds received a bye into the second round.