On July 4, 2010, Jiménez was one of two Rockies, along with shortstop Troy Tulowitzki, selected as a National League All-Star to play in the 2010 Major League Baseball All-Star Game at Angel Stadium of Anaheim in Anaheim, California. He entered the game leading all Major League pitchers with a 15–1 record and a 2.20 ERA (as of July 8). On July 12, 2010, Jiménez was named the starting pitcher for the National League All-Star team ahead of fellow NL aces Tim Lincecum, Roy Halladay, and Adam Wainwright. In two scoreless innings he threw 25 pitches with two hits, one strikeout, one walk, and 3 baserunners. 2010 was the NL's first All-Star win since 1996 and Jiménez's first All-Star selection. Jiménez would finish the season on a rough note, going 4–7 after the All star break. Jiménez finished 19–8 and an ERA of 2.88 in 221.1 innings pitched for the Rockies.