Jamie Roberts has been given a chance to avenge Wales' defeat by New Zealand last month after being selected at inside centre by the Barbarians.
The Baa-Baas face the All Blacks, who prevailed 19-12 at the Millennium Stadium, at Twickenham on Saturday in their now traditional end of autumn fixture.
British & Irish Lions star Roberts is picked alongside fellow Welsh internationals Andy Powell and Leigh Halfpenny, who feature among the replacements.
Springbok lock Victor Matfield will captain a side containing 925 caps, heading a seven-strong South African contingent that includes the uncapped WP Nel.
Bryan Habana starts on the left wing while All Black Joe Rokocoko has been handed the number 14 jersey against his national team-mates.
Australia supply four players to the starting line-up, including skipper Rocky Elsom and fly-half Matt Giteau.
Barbarians coach Nick Mallett said: "We have the benefit of a full week together ahead of the match.
"Knowing the talent that has been assembled among the 22 players, we expect to be very competitive and give the All Blacks and the Twickenham crowd a real taste of Barbarian rugby at its best."
D Mitchell (Australia); J Rokocoko (New Zealand), J Fourie (South Africa), J Roberts (Wales), B Habana (South Africa); M Giteau (Australia), F du Preez (South Africa); S Perugini (Italy), B du Plessis (South Africa), W P Nel (uncapped), C del Fava (Italy), V Matfield (South Africa, captain), R Elsom (Australia), S Burger (South Africa), G Smith (Australia).
S Moore (Australia), T Mtawarira (South Africa), Q Geldenhuys (Italy), A Powell (Wales), W Genia (Australia), M Steyn (South Africa), L Halfpenny (Wales).