Jiménez earned his first MLB win on July 29, 2007 at home against the Los Angeles Dodgers. He pitched six innings, giving up four hits and two earned runs. The Rockies won the game, 9–6. On September 5, he gained the distinction of giving up Barry Bonds's 762nd and final career home run. Jiménez made his Major League Baseball postseason debut on October 6 during Game 3 of the 2007 National League Division Series in Colorado against the Philadelphia Phillies. He started the game and pitched six innings, allowing three hits and one earned run, as part of a 2–1 victory (the win gave the Rockies a series sweep over the Phillies). However, Jiménez didn't receive a decision for the game. He started his second consecutive game of the postseason on October 12, which was Game 2 of the 2007 National League Championship Series against the Arizona Diamondbacks on the road. He pitched five innings, giving up one hit and one earned run. The Rockies would eventually win the game, 3–2, but Jiménez received his second straight postseason no-decision. Colorado swept Arizona and faced the Boston Red Sox in the 2007 World Series. Jiménez started Game 2, suffering a 2–1 loss in Boston. He allowed three hits and two earned runs in innings. Boston went on to sweep Colorado.