Looking forward to the encounter, the 2005 Lions captain said: "Having previously played for the Barbarians against the Springboks in Cardiff seven years ago and also enjoyed their tour to Scotland and England in 2004, it is a great honour for me to be invited to captain the club for what promises to be another great game against South Africa.
â00I have very happy memories of playing for the Baa-Baas against England at Twickenham three years ago and look forward to returning there in December."
O'Driscoll's appointment adds to the Irish interest in the fixture with Ireland coach Eddie O'Sullivan already pencilled in to coach the Baa-Baas for the December date.
O'Driscoll added: "I'm really looking forward to preparing for the match with Eddie as coach and the prospect of many world class players from several countries as team-mates."
Lining up some of world rugby's biggest stars, the Barbarian Football club have invited Jerry Collins and Sitiveni Sivivatu from New Zealand, Chris Latham, Matt Giteau and Rocky Elsom from Australia and Argentina's Juan Martin Hernandez and Mario Ledesma to take part.
Stars from closer to home include Englandâ00s Jason Robinson and Andrew Sheridan, French powerhouse Sebastien Chabal and the captainâ00s Ireland team-mate Paul Oâ00Connell, while Martyn Williams and Tom Shanklin from Wales have also been invited.
The match at Twickenham will be the Barbarians' sixth fixture with South Africa. The Baa-Baas won 6-0 at Cardiff Arms Park in 1961 and 23-15 at Lansdowne Road in 1994. Tickets for the game are now available from www.Ticketmaster.co.uk, starting at STGÂ£25.00.