Aryna Sabalenka defeated by Karolina Muchova in Paris semi-finals
Ranked 43rd in the world, Muchova won 7-6 (7-5) 6-7 (5-7) 7-5 after saving a match point at 5-2 in the decider.
Muchova, 26, will play either Polish top seed Iga Swiatek or Brazilian 14th seed Beatriz Haddad Maia on Saturday.
Defending champion Swiatek faces Haddad Maia in Thursday's second semi-final.
Sabalenka's exit means 22-year-old Swiatek will remain world number one, a position she has held for 62 consecutive weeks, if she beats Haddad Maia and reaches the final.
Sabalenka, 25, served for the match in the decider but was overcome with tension as Muchova kept her composure to win an epic in three hours and 13 minutes.
"I don't know what happened," said Muchova, the fourth lowest-ranked woman to reach the final after Iga Swiatek, Jelena Ostapenko and Renata Tomanova.
"It is unbelievable. I tried to keep fighting, and it worked. I'm so happy."
Muchova covered her face with a towel as she sat and contemplated the magnitude of her achievement, a stark contrast to when she sobbed on her chair at Roland Garros last year after having to retire injured from her third-round match.
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