Ospreys prop Ryan Bevington and Dragons back row forward Toby Faletau make their debuts and become Wales' 1,081st and 1,082nd internationals respectively while there are three other uncapped players, Dragons hooker Lloyd Burns, Blues prop Scott Andrews and Scarlets centre Scott Williams, selected on the bench.
Henson, who like Jones is a double Grand Slam winner (2005, 2008), returns to form a new midfield partnership with Scarlets centre Jonathan Davies and add to his 31 caps, after last playing for Wales in the 2009 RBS Six Nations 15-17 home defeat to Ireland.
Mike Phillips (Ospreys) resumes his established international half-back partnership with Scarlets fly-half Jones and Dragons wing Aled Brew joins Scarlets pair George North (wing) and Morgan Stoddart (full-back) to complete the back line.
Up front No8 Faletau debuts in a young back row alongside captain Sam Warburton (Blues) and fellow Dragon Dan Lydiate.
It's an all-Ospeys front row as Bevington makes his first appearance for Wales in familiar company alongside hooker Huw Bennett and prop Paul James with Dragons lock Luke Charteris and another experienced Osprey, 51-times capped Ryan Jones, forming the second row.
"Stephen has reached a fantastic milestone and he deserves all the plaudits he will get, but he is so important to us and will continue to be so in the coming months that there is also a sense that it is great for us to get his 100thcap out of the way," said national coach Warren Gatland.
"He still has so much more to give and it is a testament to him that he is still hungry, he is not limping towards a century of caps with a sense of relief, but bursting through the landmark, relishing the Baa-Baas game, but then intent on focussing on the World Cup and the matches ahead.
"We have tried to get the right mixture of youth and experience in there and I'd like to think the likes of Ryan Bevington and Toby Faletau will look at this and think 'this is a good chance for me'."
Elsewhere, alongside the three potential new caps on the bench Alun Wyn Jones (Ospreys) and Josh Turnbull (Scarlets) provide second and back row cover and Scarlets duo Tavis Knoyle (scrum-half) and Rhys Priestland (fly-half) complete the replacements.
"You only have to look at the quality and the experience in the Barbarians squad to know that we are looking at a huge challenge this weekend,"added Gatland.
"It's a psychological challenge that we need to be prepared for, there is a lot at stake for all of us and for the players in particular in terms of us assessing their character and them booking their places on that plane for the Rugby World Cup.
"It's an opportunity for players like Gavin (Henson) to do his talking on the rugby pitch. We have Andrew Bishop, Jamie Roberts, Jonathan Davies and now Scott Williams, but we need depth and hopefully Gavin does well and he puts some pressure on the established guys.
"He tells us it's fantastic to be back in this environment, that he has really missed it and is loving his rugby at the moment and that's a real positive for us, he knows he just needs to let his rugby do the talking now."
WALES: Morgan Stoddart; George North, Jonathan Davies, Gavin Henson, Aled Brew; Stephen Jones, Mike Phillips; Ryan Bevington, Huw Bennett, Paul James, Ryan Jones, Luke Charteris, Dan Lydiate, Sam Warburton (Captain), Toby Faletau.
REPLACEMENTS: Lloyd Burns, Scott Andrews, Alun Wyn Jones, Josh Turnbull, Tavis Knoyle, Rhys Priestland, Scott Williams.