Top-seeded Sabalenka defeated American Coco Gauff 7-6 (7-5), 6-2 in the final match of the round-robin stage at the King Saud University Indoor Arena, dashing her title hopes.
Belarus Sabalenka topped the Stefanie Graf Group with a perfect 3-0 record, while Pegula defeated eighth-seeded Jasmine Paolini of Italy 6-2, 6-3 to finish runner-up.
Sabalenka will face fourth-seeded American Amanda Anisimova in the US Open final, while Pegula will face sixth-seeded Elena Rybakina of Kazakhstan in the semifinals on Friday.
"She's always making me work hard, always great battles against her, I enjoy fighting against her," said Sabalenka, who lost to Anisimova in the Wimbledon semifinals before beating her in the U.S. Open final. "I'm super excited to face her in the semis."
This was the 12th career meeting between the two, in which Sabalenka twice overcame a one-break deficit against Gauff to force a tiebreaker, and the Belarusian won the first set in 55 minutes.
The four-time major champion raced to a 4-0 lead in the second set and, despite a brief comeback from Gauff, who narrowed the gap to one break, managed to regain control of the match and reach the last four.
"I was just trying to stay aggressive, to find my rhythm, find my game," Sabalenka said of her opening set struggles against Gauff. "I was kind of working for the second set already, but I was able to turn it around.
"I'm happy to make it through the round robin stage."
Earlier in the day, Pegula defeated Paolini and, in the process, avenged her recent defeat against the world No. 8 at the Billie Jean King Cup Finals in Shenzhen.
"I'm really happy and excited to be through into the semis here," she said. "I knew I needed to win today, especially in straight sets, so that was kind of my main motivation and I'm glad I was able to play some really good tennis."
The former U.S. Open finalist is competing in the WTA Finals for a fourth consecutive season and believes the caliber of the field this year has been stronger than previous ones.
"I felt like this year was so competitive," Pegula said. "I felt like this group has been so strong all year and we've all had a time of the year where we've played such a high level.
"I do feel like the level has been crazy, crazy deep this year. It feels a little bit harder than maybe past years."
With Gauff and Poland's Iga Swiatek both out of the competition, a first-time WTA Finals champion will be crowned on Saturday in Riyadh.
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