The 26-year-old Belgian, who has come out of retirement to play in her first Grand Slam since the 2007 Australian Open, made a confident start.
Li briefly rallied in the second set but a series of errors sealed her fate.
Clijsters will next play Williams after the American beat Italy's Flavia Pennetta 6-4 6-3 in the night session.
Pennetta has been on great form and provided a stern test but Williams is at the top of her game, and a single break in each set was enough for her to win in one hour 15 minutes.
By beating Li, from China, Clijsters has equalled the best performance by a women's wildcard in a Grand Slam - Zheng Jie's run to the Wimbledon semi-finals in 2008.
The 2005 US Open champion took two years out of the game from May 2007, during which time she gave birth to daughter Jada Ellie, and only returned to competitive action in August this year.
Clijsters, a former world number one, does not have a WTA ranking but will leap back into the top 50 after her run at Flushing Meadows, which has seen her beat Venus Williams and Marion Bartoli.
She started solidly against Li and, apart from a blip midway through the second set when she lost three games in a row to trail 4-3, always looked comfortable.
"I'm glad I got through it again, and stayed focused on my game," Clijsters said afterwards.
"I wanted to be aggressive and I think that's what helped winning those important points today."
Li says she is not surprised by Clijsters' form, explaining: "I saw her when she came back in her first tournament. I knew she was at a high level.
"She's much stronger than other girls, so I knew, if she was going to come back, it must be a strong comeback."
Clijsters played in only two tournaments before coming to Flushing Meadows - in Cincinnati and Toronto last month.
She admits she is surprised to be in the last four so soon after launching her comeback but still feels she is capable of reaching and winning Saturday's final.
"Something switched with me after Toronto where I felt like, 'Okay, I can compete with these girls.' That was obviously a big question in my mind," Clijsters explained.
"Although I was hitting the balls really good in practice and I felt physically I was doing well, you still want to know what it's like to play against those girls and get a feel for how the level has changed, how girls are playing different tennis maybe these days.
"But I never had that kind of mentality before this tournament, thinking that I was going to get to a semi-final or final.
"So I am surprised that I'm sitting here talking to you right now, but I'm very happy, and, you know, flattered that I get to do that."
In the girls' tournament, British number one Laura Robson reached the third round with a 4-6 6-1 6-4 win over Lauren Embree of the United States and will next play Tamaryn Hendler of Belgium or Yulia Putintseva of Russia.
Another British girl, Heather Watson, takes on Courtney Dolehide of the US in her third-round match on Wednesday.
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