The French Open champion, who was making her second appearance at the Wuhan Open, trailed 3-0 in the second set but dug deep to reduce the deficit to 5-3 before claiming four straight games to seal victory.
At 5-4, Pegula had the chance to force a final-set decider on serve but was broken emphatically by a relentless Gauff.
“You’re the three-set queen,” she told Pegula on court, “so I was determined not to let you get there today because I felt like the odds would be in your favour in the third set.”
Pegula had played in final-set deciders in all eight of her previous matches at the Wuhan Open, while Gauff had finished off all of hers in straight sets.
“It’s an honour to play you, as a friend and fellow American in the final,” added a gracious Pegula.
“It’s our first final, so that was a lot of fun being able to play.”