Ulster's former Wallaby lock Justin Harrison is also set to make an appearance for the invitational outfit.
The team will be captained by Bristol and England hooker Mark Regan, who played for the Baa Baas against England in 2005 and 2006.
Due to a clash with fixtures in the Magners League and EDF Energy Cup this weekend, there is a high number of Southern Hemisphere players in the Barbarians squad, including Matt Giteau, Justin Marshall, Conrad Smith, Joe Rokocoko, Ma'a Nonu, Troy Flavell, Rocky Elsom and Jerry Collins.
In all, seven nationalities are represented, including four players from both England and Wales, and Saturday's game will give the anticipated 58,000-strong crowd the opportunity to bid farewell to England full-back Jason Robinson in his final first-class appearance.
The Baa Baas will be holding two training sessions - at London clubs Blackheath and Richmond - this week in the lead-up to the clash with the Springboks.
The match is the Barbarians' sixth game against South Africa. The Barbarians defeated the 'Boks at Cardiff Arms Park in 1961 and at Lansdowne Road in 1994.
BARBARIANS Squad (v South Africa): Backs (10) - Jason Robinson (England), Joe Rokocoko (Blues/New Zealand), Isoa Neivua (Warriors/Fiji), Ben Cohen (England), Conrad Smith (Hurricanes/New Zealand), Tom Shanklin (Cardiff Blues/Wales), Ma'a Nonu (Hurricanes/New Zealand), Matt Giteau (Western Force/Australia), Peter Grant (Stormers), Justin Marshall (Ospreys/New Zealand).
Forwards (12) - Andrew Sheridan (Sale Sharks/England), Federico Pucciarello (Munster/Italy), Salesi Ma'afu (Brumbies), Mark Regan (Bristol/England) (capt), Schalk Brits (Stormers), Brent Cockbain (Wales), Justin Harrison (Ulster/Australia), Luke Charteris (Newport Gwent Dragons/Wales), Troy Flavell (Blues/New Zealand), Jerry Collins (Hurricanes/New Zealand), Martyn Williams (Cardiff Blues/Wales), Rocky Elsom (Waratahs/Australia).