The two-time Grand Slam star has not pulled on the red of his country since March 2009 when he faced Ireland in the RBS 6 Nations.
The 29-year-old is one of six Lions named in Warren Gatland's youthful 26-man squad. Wales will be captained by Cardiff Blues flanker Sam Warburton, a player who has been hotly tipped for a place on the 2013 Lions tour of Australia.
He will lock horns with his regional teammate and rival for the number seven jersey Martyn Williams, a three-tour Lion, who will turn out for the Baa-Baas.
"Sam Warburton takes over the captaincy mantle from Matthew Rees, who is rested. Sam is one of the leaders in the squad and will benefit from the experience of captaining the side after having such an impressive Six Nations campaign," said Gatland.
Wales have named five uncapped players in the squad namely Newport Gwent Dragons pair Lloyd Burns and Toby Faletau, Scarlets duo Lou Reed and Scott Williams and Ospreys prop Ryan Bevington.
Two-tour Lion Stephen Jones is also included and is set to join fellow 2005 tourist Gareth Thomas as the most capped player in Welsh rugby history by making his 100th.
"We have selected some exciting youngsters who have been chosen on form in the knowledge that there are a few players who are being rested or are injured for this game, but it means they have a chance to impress," added Gatland.
"It's a great opportunity for us to look at some players that have been hitting their form over the last few weeks.
"These are really exciting times for us as a squad, the Rugby World Cup is on the horizon and we begin our preparations with this first up match against the Barbarians before two intensive training camps in Poland and then our final three matches in August."
Wales squad to face the Barbarians on June 4:
*Bold denotes a former British & Irish Lion
Forwards: P James, J Yapp, R Bevington, S Andrews, H Bennett, R Hibbard, Lloyd Burns, A W Jones, R Jones, L Charteris, L Reed, D Lydiate, T Faletau, J Turnbull, S Warburton (capt)
Backs: M Phillips, T Knoyle, S Jones, R Priestland, G Henson, Scott Williams, J Davies, Shane Williams, A Brew, G North, M Stoddart.