Ana Ivanovic did not defend her title this year for two reasons: She did not win, or reach, a single final this year in order to gain direct acceptance, and she did not receive a wild card due to her participation in the 2012 Fed Cup finals.

The singles draw saw eight women qualify from the year, and began as a round robin event, split into two groups of four, with the top four ranked players seeded.

The six highest-ranked players who have captured at least one International tournament during the year and who are not participating in singles at the year-end WTA Championships in Istanbul or the finals of the Fed Cup will automatically qualify for the event.

[4] She did not reach a final until the e-Boks Open, where she was the two-time defending champion but lost to Angelique Kerber 4–6, 4–6.

[7] At the US Open, after reaching the semifinals the previous year, she lost in the first round 2-6, 2-6, which dropped her ranking out of the top 10 for the first time since 2009.

[8] She won her first title of the year at KDB Korea Open, defeating Kaia Kanepi 6-1, 6-0.

[9] A few weeks later, she continued her good form and won the title at Kremlin Cup, claiming victory over Samantha Stosur 6–2, 4–6, 7–5, coming back from 1–4 in the final set.

She qualified for the event by winning the UNICEF Open, her first grass title defeating Urszula Radwańska 6-4, 6-3 in the final.

[17] She reached her second final at the New Haven Open at Yale losing to Petra Kvitová 6-7(9-11), 5-7, despite leading 5-2 in the second set.

She qualified to the event by winning the Texas Tennis Open defeating Jelena Janković 7-5, 6-3 in the final and without dropping a set in the tournament.

This made her eligible to qualify for the event[28] She also won the Guangzhou International Women's Open defeating Britain's Laura Robson 6-3, 5-7, 6-4, after coming back from 0-3 in the deciding set.

[35] Zheng was able to participate because of the earlier injury-induced withdrawal of qualifier Kaia Kanepi, who was higher ranked.

Hantuchová was the last player to gain direct acceptance to Sofia after qualifier Venus Williams decided not to participate due to other commitments.

[44][45] The 2012 edition of the Tournament of Champion, the competitors were divided into two groups the Sredets and Serdika, which are districts in Sofia.

[46] In the Serdika group, in their respective head-to-heads, Caroline Wozniacki was 7-2, Roberta Vinci was 4-2, Hsieh Su-wei was 0-4, and Daniela Hantuchová was 4-7.

Leading the group Wozniacki is down in her head-to-head against Vinci 0-1, losing their only encounter at the 2011 Rogers Cup 6-4, 7-5.

Wozniacki also has a good record against Hantuchová, as she led 5-1, with her beating the Slovak twice in the year, with the latest win coming at the 2012 Toray Pan Pacific Open 7-6(7-3), 6-1.

Vinci on the other hand has a 1-0 record against Hsieh, with the win coming in the 2012 Dallas Tennis Classic 6-2, 6-2.

In the final head-to-head of the group between Hantuchová and Hsieh, the Slovak leads 1-0 with the win coming in the 2012 PTT Pattaya Open 6-4, 6-1.

Kirilenko on the other hand is 3-5 down against Zheng in their head-to-head, however she won their last 2 meeting both in 2012, with the latest encounter at the 2012 Mutua Madrid Open 6-2, 7-5.