Teherán signed a 6-year, $32.4 million extension with the Braves on February 14, 2014. He was the Braves' Opening Day starter for the first time in his career, taking the loss in a 2–0 game against the Milwaukee Brewers. Teherán was selected to the 2014 MLB All-Star Game, his first All-Star Game selection. However, he was ineligible due to previously pitching the Sunday before the All-Star break. He was honored as an All-Star in a pregame ceremony. Teherán became the second Colombian to be selected an All-Star, following former Braves player Édgar Rentería. In 33 starts on the season, Teheran went 14–13 with a 2.89 ERA, a 1.08 WHIP, and 186 strikeouts in 221 innings.
Teherán throws a four seam fastball that averages 92 mph, paired with a two seam fastball at 89 mph. His slider and change up both are thrown at around 82 mph. His curveball sits in the mid-70s. Teherán also has a screwball (65 mph) that he does not use very often. Teherán has a very effective pickoff move. His 22 successful attempts in 2014 through early September was the most for any pitcher during that period.