The Reds had lost five in a row, but they cooled off baseball's hottest team thanks to a seven-inning effort from Volquez (10-2). He allowed two runs on seven hits and struck out five.
Volquez leads the majors with a 1.71 ERA. Francisco Cordero came on in the ninth for his 14th save.
Jolbert Cabrera had a two-run double during Cincinnati's three-run fifth inning. He went four for four before leaving the game with a dislocated left index finger, suffered while making a headfirst slide while advancing on a wild pitch in the seventh.
Joey Votto added a homer among his three hits.
Mike Mussina suffered his first loss since May 20. Mussina (10-5) surrendered four runs on 10 hits in eight innings.
It was Cincinnati's first appearance in Yankee Stadium since the Reds swept New York in the 1976 World Series.