At the 2012 London Olympics, Li, seeded 10th, crashed out in the first round to Slovakian Daniela Hantuchová. Her poor performance caused her to drop out of the world top ten for the second time in the year following the conclusion of the Games. After the Olympics, Li announced that she and Carlos Rodríguez, coach of former world No. 1 and seven-time major winner Justine Henin, have commenced a coaching relationship.