Sanne Wevers of the Netherlands pushed past Simone Biles and Laurie Hernandez to win gold for balance beam with a 15.466 at the Rio Games on Monday.
The current reigning world champion in beam, Biles stumbled during a front summersault on the beam after her right foot slipped off, but she did not fall.
Biles had been aiming to become the first female to win five gymnastics gold medals in a single Games, but her sparkling run finally came to an end after victories in the team and individual all-around competitions as well as the vault.
She goes after a fourth gold in the floor event on Wednesday.
Wevers - the Netherlands' first beam competitor in Olympic history - beat Hernandez by just 0.133 of a point, with Biles lagging behind in third with 14.733.
The top three faced an anxious wait in the auditorium as France's fourth-placed Marine Boyer submitted an inquiry on her routine, but it was rejected to spare Biles' blushes somewhat.
World and European champion Eleftherios Petrounias won the men's rings earlier on Monday, an even 16.000 enough to continue his dominance of the event.
Brazil's Arthur Zanetti took silver - becoming his country's first multi-medallist in gymnastics - while Denis Abliazin took bronze.
"I think Greece always has some problems and hard times, but in the end we always make it happen," Petrounias said.
"I am really thankful for being a Greek, even with hard times. I feel like a part of the Olympics, as we brought the Olympics. I am happy to do something for my country."
North Korea's two-time vault world champion Ri Se-gwang also backed up his pedigree at the Olympics, with a narrow event win ahead of Abliazin, whose silver represented a fifth Olympic medal, making him Russia's second most successful gymnast. Kenzo Shirai of Japan took bronze.