The 92-Test capped Australian leads an experienced line-up which was named by coach Nick Mallett in Cape Town on Thursday.
The 23-man match-day squad also included three non-capped South African players in prop Schalk Ferreira, hooker Craig Burden and scrumhalf Rory Kockott.
The World XV’s half-back pairing of Giteau and Kockott were on opposite sides last week when they played for Toulon and Castres, respectively, in the French Top 14 final at Stade de France.
Giteau would be joined by his Toulon team-mates Burden, prop Carl Hayman, wing Drew Mitchell and flank Steffon Armitage.
Mallett said his main objective was ensuring that his team would be competitive to do justice to the event.
“What the World XV players can offer is the willingness to be physical and to be courageous on defence,” Mallett said.
“The Boks are direct and will put you under pressure when it comes to sheer physicality. The Boks improved their attack last year but they have not moved away from physicality.”
World XV team: James O’Connor, Drew Mitchell, Rene Ranger, Wynand Olivier, Hosea Gear, Matthew Giteau (captain), Rory Kockott, Roger Wilson, Steffon Armitage, Mamuka Gorgodze, Alistair Hargreaves, Juandre Kruger, Carl Hayman, Craig Burden, Fakaanaua Taumalolo.
Replacements: Andrew Hore, Schalk Ferreira, Pat Cilliers, Iosefa Tekori, Alexandre Lapandry, Jimmy Cowan, Francois Trinh-Duc, Benson Stanley.