After the 2013 season, Vólquez signed a one-year deal worth $5 million with the Pittsburgh Pirates. Volquez experienced a career rebirth with the Pirates, going 13–7 with a 3.04 ERA and 140 strikeouts in 32 games (31 starts), pitching innings. On October 1, 2014. Vólquez started the 2014 National League Wild Card Game for the Pirates against the San Francisco Giants. Vólquez would not come through however, giving up 5 ERs, including a grand slam to Giants shortstop Brandon Crawford, in 5 innings pitched. The Pirates would go on to lose 8–0, eliminating them from the playoffs in the process. The Wild Card Game would prove to be Volquez's last game as a Pirate, as he became a free agent after the 2014 season.