Smit, who led the Boks to World Cup glory in 2007 and a nail-biting series triumph over the Lions two year later, will win his 100th cap in the historic Tri Nations encounter at the Soccer City stadium in Soweto.
"The whole week I have tried to put the 100th game in the background and make sure the team interest comes first," said Smit, whose Bok side desperately need a win over the All Blacks to keep their Tri Nations hopes alive.
"It is fantastic to reach 100 Tests and even more special to be playing the game against the All Blacks.
"It is a great honour but there are times when the milestone is less significant than the people who played a role in getting you there.
"There have been many highlights and also some low points but the successes have more than made up for the disappointments."
The 32-year-old, who made his Test debut a decade ago and assumed his country's captaincy in 2004, will become only the second South African to reach the landmark.
Smit will join former Newport star Percy Montgomery in a list of 15 players to have reached a century of caps.
There are five Lions on that list, with triple tourist Jason Leonard second behind Australia's George Gregan who made a staggering 139 appearances for the Wallabies.
Brian O'Driscoll, John Hayes and Ronan O'Gara all passed the landmark for Ireland and the Lions last season, while Gareth Thomas, who skippered the Lions in O'Driscoll's absence in 2005, is also included.
Fellow Lions Martyn Williams and Stephen Jones also look set to join that list this autumn, with the Welsh pair currently sitting on 99 and 97 caps respectively.
The 100 Club
George Gregan (Australia) 139 caps
Jason Leonard (England and the Lions) 119
Fabien Pelous (France) 118
Philippe Sella (France) 111
George Smith (Australia) 110
Brian O'Driscoll (Ireland and the Lions) 109
John Hayes (Ireland and the Lions) 104
Gareth Thomas (Wales and the Lions) 103
Stephen Larkham (Australia) 102
Percy Montgomery (South Africa) 102
David Campese (Australia) 101
Ronan O'Gara (Ireland and the Lions) 101
Alessandro Troncon (Italy) 101
Chris Paterson (Scotland) 100
NB. Bold denotes Lion