Zimbabwe included Heath Streak and Andy Blignaut, both making their first Test appearances since the player row that stripped the team of many of its leading players last year.
South Africa showed two changes from the side that drew the fifth Test against England in January.
Batsman Ashwell Prince returned for his first Test since the 2002/03 season in place of all-rounder Andrew Hall, while swing bowler Charl Langeveldt returned to the side for the first time since breaking a bone in his left hand while making his debut in the third Test against England, also at Newlands.
Langeveldt played in place of Andre Nel, who was released from the squad to play in a domestic match after suffering from a hamstring strain.
On a hot sunny day, the pitch looked good for batting, although with slightly more grass than usual.
Graeme Smith (captain), AB de Villiers, Jacques Rudolph, Jacques Kallis, Herschelle Gibbs, Ashwell Prince, Mark Boucher, Shaun Pollock, Nicky Boje, Makhaya Ntini, Andre Nel, Charl Langeveldt
Tatenda Taibu (capt), Stuart Matsikenyeri, Barney Rogers, Dion Ebrahim, Hamilton Masakadza, Brendan Taylor, Heath Streak, Elton Chigumbura, Andy Blignaut, Alexander Cremer, Christopher Mpofu
Umpires: Billy Bowden (NZL), Billy Doctrove (WIS). TV umpire: Brian Jerling (RSA). Match referee: Alan Hurst (AUS).