Williams, a seven-time Grand Slam winner and the No. 6 seed in the tournament, won 3-6, 6-2, 6-1 in a match that lasted just under 2 hours.
The U.S. star has advanced at least as far as the quarterfinals seven times in the Australian Open, but she has not won it.
Schiavone has made it to the quarterfinals of the other three majors, but not in Melbourne.
Williams next plays No. 16 Li Na of China, who moved into the quarters with a 6-4, 6-3 upset of No. 4 Carolina Wozniacki of Denmark.
Top-seeded and defending champion Serena Williams, Venus' younger sister, was scheduled to play 13th-seeded Samantha Stosur of Australia later Monday.
The Williams sisters were on track to meet in the semifinals.
Copyright 2010 by United Press International.
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