Li started her 2012 season in the Hopman Cup with countryman Wu Di, who was also from Hubei Province, where she won all three single rubbers against Marion Bartoli, Anabel Medina Garrigues and Jarmila Gajdošová. It was her first win over Anabel Medina Garrigues in four meetings. It was a return to her form after being plagued by losses and early round exits in almost all her tournaments during the second half of 2011 following her Roland Garros triumph. Li then played in the Sydney to defend her title. She defeated Ekaterina Makarova, Chanelle Scheepers and Lucie Šafářová to reach the semifinals. In the semifinal, she came back from one set down to eke out the win against world No. 2 Petra Kvitová, the favorite to win the tournament. In the final, Li failed to defend her title, losing the match to Victoria Azarenka in three sets.