In a May 27 game against the San Diego Padres at Petco Park in San Diego with the Cardinals holding a 4–3 lead in the bottom of the ninth, Molina picked Brian Giles off first to end the game, the first pickoff to end a major league game in nearly four years. The Cardinals faced the Padres again in the National League Division Series (NLDS) playoff game in the playoffs, he again picked a Padre off at first, this time Mike Piazza, while bailing pitcher Jeff Suppan out of a jam. For the season, he caught 41% of all base-stealing attempts and picked off seven runners.