However the retired former Magpie, Demon and Swan will be coaching rather than playing alongside the Saints' young ruckmen, after accepting a part-time position under new head coach Alan Richardson.
St Kilda finalised its coaching appointments for the 2014 season on Saturday, with former Western Bulldog Lindsay Gilbee becoming the club's development coach and Simon McPhee appointed manager of the player academy.
Jolly looked a likely candidate to join the Saints after the 2013 player exchange period but was not selected in the rookie draft and subsequently announced his retirement.
Welcoming Gilbee and Jolly to St Kilda, the club's head of football Chris Pelchen said the experienced pair would be a perfect fit to work with the young list.
“Lindsay and Darren bring a wealth of football experience to their new roles and both will be wonderful assets to our club,” Pelchen said.
Jolly will work with the club's relatively untried ruck department, including new recruit Billy Longer and international rookie Jason Holmes.
Dual premiership player Jolly played 237 games in a 13-year career atthe Demons (48 games), the Swans (118) and the Magpies (71). He was amember of premiership teams in Sydney in 2005 and Collingwood in 2010.
His delisting from Collingwood at the end of the 2013 season caused an acrimonious fallout with Nathan Buckley over the reasons for Jolly's departure.
Gilbee played 206 games for the Bulldogs from 2001 to 2012. A right-footer who was considered one of the best kicks in the game in his time, he was named an All Australian in 2006 and finished third in the Bulldogs’ best and fairest in 2005.
He represented Australia in the International Rules series in 2005 and 2006.