The 32 year old will be joined in the back row by European Player of he Year Steffon Armitage and Montpellier's Mamuka Gorgodze. World stars such as Matt Giteau, Hosea Gear, James O'Connor and Carl Hayman will also feature for the invitational team.
Ulster colleague Ruan Pienaar will operate at scrumhalf for the Springboks, who have opted for an experienced side.
South Africa: 15 Willie le Roux, 14 Cornal Hendricks, 13 JP Pietersen, 12 Frans Steyn, 11 Bryan Habana, 10 Morne Steyn, 9 Ruan Pienaar, 8 Duane Vermeulen, 7 Willem Alberts, 6 Francois Louw, 5 Victor Matfield (c), 4 Bakkies Botha, 3 Jannie du Plessis, 2 Bismarck du Plessis, 1 Tendai Mtawarira.
Replacements: 16 Schalk Brits, 17 Gurthro Steenkamp, 18 Coenie Oosthuizen, 19 Flip van der Merwe, 20 Schalk Burger, 21 Fourie du Preez, 22 Johan Goosen, 23 Lwazi Mvovo.
World XV: 15 James O'Connor, 14 Drew Mitchell, 13 Rene Ranger, 12 Wynand Olivier, 11 Hosea Gear, 10 Matt Giteau, 9 Rory Kockott, 8 Roger Wilson, 7 Steffon Armitage, 6 Mamuka Gorgodze, 5 Alistair Hargreaves, 4 Juandré Kruger, 3 Carl Hayman, 2 Craig Burden, 1 Sona Taumalolo.
Replacements: 16 Andrew Hore, 17 Schalk Ferreira, 18 Pat Cilliers, 19 Joe Tekori, 20 Alexandre Lapandry, 21 Jimmy Cowan, 22 François Trinh-Duc, 23 Benson Stanley.
Match details:
Date: Saturday, June 7
Kick-off: 16:00 GMT
Venue: Newlands, Cape Town