"This is a signal moment for CSA and particularly for the 79 cricketers who have carried the Proteas emblem into the Test match arena," said CSA Acting CEO Jacques Faul.
"It is particularly fitting that it should happen in a match where there is so much at stake and where there is such eager anticipation around the cricketing world with the No.1 Test match ranking at stake between ourselves and Australia," he added.
"It seems only yesterday that Kepler Wessels led the Proteas into a Test match for the first time in the West Indies - a match in which Andrew Hudson, our current convener of selectors, scored a Test century on debut.
"There have been so many highlights since then and everybody will have their own particular favourite. Suffice to say that the Proteas brand is hugely respected around the cricketing world.
Smith, who made 151 and shared a first-wicket partnership record of 368 with Herschelle Gibbs in the Proteas' 100th Test match against Pakistan at Sahara Park Newlands in 2003, will be leading the Proteas for the 96th time.
The other Test match captains have been: Hansie Cronje (53 matches), Shaun Pollock (26), Kepler Wessels (16), Mark Boucher (4), Jacques Kallis (2), Ashwell Prince (2), Gary Kirsten (1).