At the 2001 world championships, he earned a bronze medal in the 50m freestyle, but his greatest success would come at the 2004 Olympic Games in Athens.
In the 4x100m freestyle relay, Schoeman, swimming the leadoff leg, put the South African team into a lead that they would never relinquish. He was followed in the pool by Lyndon Ferns, Darian Townsend and Ryk Neethling. When Neethling touched the wall to complete the race, the South Africans had not only won by 1.19 seconds, they had broken the world and the Olympic records set at the last edition of the Games.
Schoeman went on to take two more medals in individual events. In the 100m freestyle, he was just edged at the end by Pieter van den Hoogenband, who beat Roland by only six hundredths of a second. Schoeman completed his set of medals with a bronze in the 50 freestyle, finishing only nine hundredths of a second behind winner Gary Hall.
In 2008 at the Beijing Olympic Games, the South African swimming relay team finished seventh in the 4x100m. In the 50m freestyle, it was a seventh place for Roland Schoeman. He did not manage to qualify for the final of the 200m medley.