The 35-year-old Cardiff Blues flanker Williams has played 10 Tests against the Springboks during his 101 cap career with Wales and the British & Irish lions, but his only success since his first outing at Wembley Stadium in 1998 was for the Lions in last year's third Test in Johannesburg.
A three times Lions tourist, he came on as a replacement for Wales in their recent 29-25 defeat by the world champions at the Millennium Stadium. It will be his fifth outing in the famous Baa-Baas jersey and his second for the club against the Boks.
He scored a try in a famous 22-5 triumph at Twickenham and will be hoping to pick up another win over a side he hopes to meet when Wales launch their World Cup campaign against the defending champions in Wellington next year.
While Williams will miss the Blues' trip to Munster for a vital Play-Off Zone clash at Thomond Park this weekend, Perugini will be absent from Aironi's trip to Connacht on Friday night.
The 74-times capped Perugini, who will have his Aironi captain and Italian team mate Quintin Geldenhuys on the replacements bench, made his Baa-Baas debut in the victory over the All Blacks at Twickenham last season
Australian outside half Matt Giteau has been handed the honour of leading the barbarians in the MasterCard Trophy match and he will be hoping to make it a hat-trick of wins over his country's two major rivals after figuring in the Baa-baas line-ups that beat the Boks in 2007 and the All Blacks last December.
In keeping with Barbarian tradition, the starting XV includes two uncapped players - Stormers skipper Anton van Zyl and Chiefs No 8 Colin Bourke. Cardiff Blues and Wales prop John Yapp is included among the replacements.
Barbarians: James O'Connor (Australia); Joe Rokocoko (New Zealand), Adam Ashley-Cooper (Australia), Ma'a Nonu (New Zealand), Drew Mitchell (Australia); Matt Giteau (Australia, captain), 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), Andrew Ellis (New Zealand), Stephen Donald (New Zealand), Seru Rabini (Fiji)
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