Then she made history seconds later by landing a second one.
Valieva, 15, performed a Quad Salchow. She followed that up with a quad toe-triple toe combination. On both, she held her hands over her head, looking like a spinning top in the air.
A salchow is when the skater, moving backward, launches from the inside edge of the left skate and lands on the outside edge of the right.
For a toe loop, the skater -- again skating backward -- starts with the outside edge of the right skate and lands on the outside edge of that same skate. The toe loop includes an assist from the toe pick on the front of the skate to take off.
Quad means she did four rotations in the air.
"We will be talking about this moment for the next 100 years," said NBC Olympics commentator Tara Lipinski.
It came one night after she became just the fourth woman to land a triple axel at an Olympic Games during the short program Saturday.
An axel is the only figure skating jump that starts with the skater facing forward. The skater launches from the outside edge of the forward skate and lands going backward on the opposite skate. Because this move requires an extra half-rotation to land backward, it's generally considered the most difficult jump.
American Mirai Nagasu was the only woman to do the triple axel at the 2018 Olympics. The other two women who have pulled it off were Japan's Mao Asada and Midori Ito.
According to Olympics.com, a quad is only allowed in the free skate. A triple axel can be performed in the short program and the free skate.
When asked if this year's Olympic podium will include a woman who doesn't do a triple axel or a quad, figure skating expert Jackie Wong, told Olympics.com, "No."
Of the three women representing the U.S., only Alysia Liu has the triple axel in her repertoire.
Thanks to a stellar performance by the ice dancing team of Madison Chock and Evan Bates in the free dance and a strong outing by Karen Chen in the women's portion Sunday, the United States won the silver in team figure skating. Japan took the bronze.
The Associated Press contributed to this report.