Devine was the Braves' first selection (27th overall) in the first round of the 2005 Amateur Draft out of North Carolina State University, where he had set the Wolfpack record for saves with 24. The selection was regarded as an unusual one for the Braves due to the fact that the organization has a history of selecting high school players with their early picks in order to have a greater hand in the players' development. After being drafted, Devine spent only two months in the minor leagues, pitching with the advanced-A Myrtle Beach Pelicans and the AA Mississippi Braves before being called up to the major leagues on August 20.
Devine encountered early struggles once being called up to the major leagues, becoming the first pitcher in major league history to allow a grand slam in each of his first two games. Braves manager Bobby Cox showed faith in Devine, however, by including him on the postseason roster despite his pitching only five innings with the big-league club during the regular season. In the 18th inning of Game 4 of the 2005 National League Division Series, Devine gave up a walk-off home run to Houston Astros rookie Chris Burke to end the Braves' season.
In 2006, Atlanta planned to have Devine start the season at AAA Richmond as the closer, but injuries to Horacio Ramírez and Blaine Boyer forced the Braves to call him up along with fellow reliever Ken Ray. Devine struggled once again, however, pitching a total of one inning in two games against the San Francisco Giants and giving up seven runs on five hits, five walks and two wild pitches. Devine was optioned back to Richmond afterwards, with Peter Moylan serving as his replacement in Atlanta's bullpen. Devine was called up again in September and continued to pitch in Atlanta until the end of the regular season. Baseball America rated Devine as the Braves' ninth-best prospect entering 2007. Devine has spent the majority of the 2007 season at Mississippi, though he has been called up by Atlanta several times (most recently September 20). On September 22, Devine earned his first major league victory against the Milwaukee Brewers. He finished the season 1-1 with a 1.08 ERA.
Signed in 2005 to the Atlanta Braves by the famous Billy Best, scout from Raleigh North Carolina