Stosur, a 2010 Roland Garros finalist, had beaten world number two Li in all six of their previous meetings.
But China's top female athlete made inroads in that one-way scoreline with her first victory, achieved in 68 minutes with five breaks of her 30-year-old rival.
Li, 32, will play a quarterfinal against Italian tenth seed Sara Errani, who beat Czech Petra Cetkovska 6-3, 7-6 (7/3).
Li finished Rome runner-up in 2012, holding a match point against eventual champion Maria Sharapova.
Australian Open champion Li is looking for her third trophy of the season as she prepares for the French Open, which she won in 2011.
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