The South African team featured four Olympic medalists from Sydney: breaststroke swimmer Terence Parkin, high jumper Hestrie Cloete, discus thrower Frantz Kruger, and hurdler Llewellyn Herbert.

Several athletes made their third consecutive Olympic appearance, including freestyle Ryk Neethling and middle distance runner Hezekiél Sepeng, who previously won the silver in Atlanta for the men's 800 metres.

Sepeng's fellow runner and teammate Mbulaeni Mulaudzi, a top medal contender on the same event, later became the nation's flag bearer in the opening ceremony.

The highlight of the South African team at these Games came with a surprising triumph in men's swimming, when Roland Mark Schoeman, Ryk Neethling, Lyndon Ferns, and Darian Townsend held a major upset on the Aussies, Americans, and the Dutch for a new world record and a prestigious gold medal in the 4 × 100 m freestyle relay.

[4] Cloete managed to repeat her silver from Sydney in the women's high jump, while Donovan Cech and Ramon di Clemente claimed a bronze for the first time in men's rowing.