Wigan and England rugby league full-back Sam Tomkins will play on the wing for the Barbarians against Australia at Twickenham on Saturday.
The 22-year-old, who will be making his union debut, is set to make a one-off appearance in the 15-a-side game.
His team-mates will include South African wing Bryan Habana, former England fly-half Danny Cipriani and Italian flanker Mauro Bergamasco.
The team will be captained by ex-Springboks lock Victor Matfield.
It also features four members of New Zealand's World Cup-winning squad, including Keven Mealamu and Jerome Kaino, with former All Blacks supremo Graham Henry coaching the invitational team.
Australia will be led by flanker David Pocock, with regular captain James Horwill - who ended the World Cup with a shoulder problem - named among the replacements.
James O'Connor, normally a wing or full-back, will start at fly-half in the absence of Quade Cooper, who damaged knee ligaments in the Wallabies' bronze medal match against Wales.
Tomkins is one of rugby league's brightest prospects and was a nominee for the coveted 2011 Super League 'Man of Steel' award.
He played for England's rugby league team in last Saturday's Four Nations 30-8 final defeat by Australia at Elland Road and his rugby league commitments are now over until the start of pre-season training with Wigan in December.
He recently signed a pledge not to talk to rugby union clubs for at least the next three years after his older brother Joel joined Saracens.
Barbarians' commercial director Mike Burton said: "We are delighted that Sam, with the support of the coaches and management at Wigan, has accepted this opportunity to play in such a high-profile union match.
"In recent years the likes of Mat Rogers, Lote Tuqiri, Wendell Sailor and, a few months ago, Willie Mason, have all made a mark when playing for us on the big stage. We are confident that Sam will be equal to the challenge this week."
Ian Lenagan, chairman and owner of the Warriors said: "The Wigan club and Sam are very pleased to accept the Barbarians' invitation.
"Sam is an exceptional player in either code of rugby and his selection shows the growing mutual respect between the codes of rugby league and rugby union in England.
"It's a great opportunity for Sam to experience the Twickenham atmosphere and showcase his talents on another major stage."
Australia have won their last seven matches against the Barbarians, their last a 55-7 thrashing of the invitational side at Sydney Football Stadium in 2009.
Barbarians team: Isaia Toeava (New Zealand); Sam Tomkins (England RL), Robbie Fruean (Crusaders), Stirling Mortlock (Australia), Bryan Habana (South Africa); Danny Cipriani (England), Peter Stringer (Ireland); Eusebio Guinazu (Argentina), Keven Mealamu (New Zealand), Sylvain Marconnet (France), Simon Shaw (England), Victor Matfield (captain, South Africa), Jerome Kaino (New Zealand), Mauro Bergamasco (Italy), Adam Thomson (New Zealand).
Replacements: Adriaan Strauss (South Africa), Salvatore Perugini (Italy), Marco Bortolami (Italy), Jason White (Scotland), Seru Rabeni (Fiji), Richard Kahui (New Zealand), Nemia Kenatale (Fiji).
Australia team: Adam Ashley-Cooper, Lachie Turner, Rob Horne, Berrick Barnes, Digby Ioane; James O'Connor, Will Genia; James Slipper, Tatafu Polota Nau, Salesi Ma'afu, Rob Simmons, Nathan Sharpe, Scott Higginbotham, David Pocock (capt), Ben McCalman.Replacements: Stephen Moore, Ben Alexander, James Horwill, Dave Dennis, Matt Hodgson, Nick Phipps, Ben Tapuai.