Before the 2009 season commenced, Molina participated with Puerto Rico in his second WBC. When the event concluded, he returned to the Cardinals. In an April 16 game against the Arizona Diamondbacks, he reached base in all five of his plate appearances in a 12–7 victory. Starting pitcher Joel Piñeiro – struggling with his fastball command in previous starts – experimented with a sinker and shut out the New York Mets on June 24 with just two hits. Molina erased a Mets runner by throwing out Luis Castillo attempting to steal second base. Molina was batting .278 with five home runs and 25 RBIs through July 5, 2009. He was selected through fan vote to represent the Cardinals in the All-Star Game in St. Louis' Busch Stadium – his first All-Star Game. As the top vote-getter among NL catchers with 2,641,467 votes, Molina was named the NL's starting catcher. He caught eight innings and drove home a run.