Pietersen was educated at the Hoërskool Generaal Hertzog in Witbank, but made his provincial debut with the Natal Sharks as a 19-year old during the 2005 Currie Cup season. His 2006 Super 14 season was disrupted by injuries but despite this, he was included in the South African under-21 team to compete at the 2006 Under 21 Rugby World Championship. South Africa made the final, but were defeated by the hosts, France. Upon arriving back to South Africa after the under-21 World Championship he was named in the Springboks' 2006 Tri Nations Series squad where he debuted against New Zealand at the Royal Bafokeng Stadium in Rustenburg.
Pietersen's deceptive pace and gliding runs make him an unpredictable back-line player, with the ability to break the line at will and create attacking opportunities for his team. He is also a clinical finisher, and was the leading try scorer in the 2007 Super 14 competition with 12 tries from 15 games. However, Pietersen's weaknesses include his occasional susceptibility to poor handling, being particularly frail protecting the "high ball" and often "knocking on" in seemingly innocuous situations, a penchant which has often led to him being chastised by the local media and fans alike. Despite this, Pietersen remains a firm fan favourite for the unpredictable and exciting dimension his play brings to the team. Before the emergence of Francois Steyn at the Sharks franchise, Pietersen was seen as the ideal replacement for Percy Montgomery as fullback, however with Steyn being able to play at either fullback, wing or fly-half, Pietersen now finds his role as play-maker in the Sharks team divided as either wing or fullback.
He was selected into the Springboks 2007 Rugby World Cup squad. Starting in the first two matches, Pietersen scored three tries. He was impressive in the game against England, scoring two tries and setting up a third.