On July 13, 2014, Simón was named to the 2014 Major League Baseball All-Star Game, replacing fellow Red Johnny Cueto, who was unavailable to pitch due to starting a game the previous Sunday. Simon was mobbed by his teammates in the dugout when the announcement was made during the game. In the All-Star game, Simón pitched a scoreless third inning, allowing one hit and striking out one batter. He would win only three more games after the All-Star break, finishing at 15–10 with a 3.44 ERA, while throwing a career-high innings.