Australia's Matt Giteau will lead the Barbarians from first five-eighth against South Africa in the world champion's tour-ender at Twickenham on Sunday.
Giteau has played twice for the invitational side but has never captained it.
"This is a great honor and I am deeply grateful to the Barbarians committee forthe confidence they have shown in me," Giteau said.
The No. 10 is one of six Australians in a strong starting lineup that also features five All Blacks.
Joe Rococoko and Australia's Drew Mitchell are on the wings outside Ma'a Nonu and Adam Ashley-Cooper. The Wallaby-dominated back line is completed by James O'Connor at fullback and scrumhalf Will Genia.
Chris Jack, Rodney So'oialo and Neemia Tialata are the other New Zealand internationals picked, with the uncapped Colin Bourke in at No. 8.
Uncapped Stormers lock Anton van Zyl goes up against his countrymen, who recovered from a shock defeat against Scotland to beat England 21-11 on Sunday, with Italy prop Salvatore Perugini and Wales flanker Martyn Williams completing the 15.
Barbarians: James O'Connor (Australia), Joe Rococoko (New Zealand), Ma'a Nonu (New Zealand), Adam Ashley-Cooper (Australia), Drew Mitchell (Australia), Matt Giteau (Australia), Will Genia (Australia); Salvatore Perugini (Italy), Stephen Moore (Australia), Neemia Tialata (New Zealand), Anton van Zyl (Stormers), Chris Jack (New Zealand), Rodney So'oialo (New Zealand), Martyn Williams (Wales), Colin Bourke (Chiefs).
Replacements: Keven Mealamu (New Zealand), John Yapp (Wales), Quintin Geldenhuys (Italy), Daniel Braid (New Zealand), Andy Ellis (New Zealand), Stephen Donald (New Zealand), Seru Rabini (Fiji).
