Devaney, who made over 170 appearances for the Reds, will join the club's Academy and aim to help bridge the gap between Under 18s and Under 21s football.
"I'm really pleased," said Devaney. "I'm really excited to get going. I can't wait to get on the grass.
"I will be assisting both Chris Howarth (Lead U18s Coach) and Paul Heckingbottom (Senior Development Coach), so that bridge between the Under 18s and Under 21s - developing the younger players.
"I want to help improve them as players and make them better prepared when they step out on Oakwell."
