World number one Williams, a 16-time Grand Slam winner seeking her fifth US Open crown and her ninth title of the year, dispatched 18th seed Carla Suarez Navarro 6-0, 6-0, in 52 minutes on the Spaniard's 25th birthday yesterday.
"I'm so happy to be in the smei-finals. It really feels great," Williams said.
Li, the 2011 French Open champion, overcame nervous feelings for a 6-4, 6-7 (5/7), 6-2 victory over Russian 24th seed Ekaterina Makarova.
"She is playing some of the best tennis of her career," Williams said. "It's going to be a tough match."
Williams, who has dropped only 13 games in five matches on the New York hardcourts, matched the worst rout in US Open women's quarter-final history, Martina Navratilova's 6-0, 6-0 blanking of Bulgarian Manuela Maleeva in 1989.
Ignoring a fan's call to let the birthday girl win at least one game and a few boos when she did not, Williams showed no mercy in taking only 52 minutes to complete the rout on a windy night at Arthur Ashe Stadium.
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