In her second appearance at the Summer Olympics, Pavlyuchenkova was the 13th seed in the singles tournament and reached her maiden Olympic quarterfinal, doing so with an Olympic record of seven games surrendered, as she saw off Sara Errani, Anna-Lena Friedsam, and Sara Sorribes Tormo. She was later defeated by the eventual gold medalist when she succumbed to ninth seed Belinda Bencic in three sets. In mixed doubles, she partnered with Andrey Rublev and the first-time pairing sailed to the final, where they took home the gold medal over compatriots Aslan Karatsev and Elena Vesnina after saving a match point.