Devine was the Braves' first selection (27th overall) in the first round of the 2005 Major League Baseball draft out of North Carolina State University, where he had set the Wolfpack record for saves with 24 and made the All-Atlantic Coast Conference team three times. After being drafted, Devine spent only two months in the minor leagues, pitching with the Single-A Advanced Myrtle Beach Pelicans and the Double-A Mississippi Braves, before being called up to the major leagues on August 20.