The match will be the final chance for Lions supporters to see the Springbok players on British soil prior to the 2009 tour of South Africa.
Uncapped South African Nick Coster, who could yet push for international inclusion against Ian McGeechan's men, has been included on a replacements bench also featuring 2005 Lions Shane Williams and Ollie Smith and 1997 tourist Mark Regan.
Jean de Villiers, Bryan Habana, Francois Steyn, Fourie du Preez, John Smit, Bakkies Botha, Johann Muller and Schalk Burger all start for the Babaas, with Smit captaining the invitational XV.
Other famous names appearing at Wembley include All Blacks Richie McCaw, Joe Rokocoko and Rico Gear, and Wallaby legend George Gregan.
"This is one of the better Barbarians side there has been for a while and Eddie and I are really chuffed to get this group of players together," said White, who led South Africa to World Cup glory last year.
"It is nice to see the players who usually smash into each other having an opportunity to play as a team and that is something unique in rugby.
"The important thing is that a number of these players haven't played for the Baa-Baas and I think it is wonderful they get the opportunity to play alongside such great players.
"A guy like Sean Fitzpatrick was a great captain of New Zealand but never got the chance to play for the Barbarians and I am sure he would have loved to play in a team like this."
Barbarians: Percy Montgomery (SA); Joe Rokocoko (NZ), Rico Gear (NZ), Jean de Villiers (SA), Bryan Habana (SA); Francois Steyn (SA), Fourie du Preez (SA); Federico Pucciariello (Ita), John Smith (SA, capt), Census Johnson (Samoa), Bakkies Botha (SA), Johann Muller (SA), Jerry Collins (NZ), Richie McCaw (NZ), Schalk Burger (SA)
Replacements: Mark Regan (Eng), Rodney Blake (Aus), Chris Jack (NZ), Nick Koster (SA, uncapped), George Gregan (Aus), Ollie Smith (Eng), Shane Williams (Wal)