Painter completed 35 of 54 passes for 546 yards and three touchdowns, boosting Purdue (8-5) to its first bowl victory in four tries.
LeFevour threw for four touchdowns and ran for two more, but the Chippewas (8-6) were unable to claim the Motor City Bowl for a second straight year. They defeated Middle Tennessee in last year's game, 31-14.
LeFevour tied the game with 74 seconds left by hitting Bryan Anderson with a 19-yard pass. It was Anderson's third touchdown catch of the night.
Painter then completed four of five passes in driving the Boilermakers from their own 39 to the Central Michigan 23 and the winning field goal.
Dustin Keller, Greg Orton and Jake Standeford all went over the 100-yard receiving mark for Purdue and each scored a touchdown.