Pietersen, who made his Test debut in the 2005 Ashes series victory over Australia, was also named as the England one-day captain in succession to Collingwood, who resigned on Sunday.
Born in Pietermaritzburg, Natal, Pietersen opted to play for the country where his mother was born because he disapproved of South Africa's racial quota system.
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He qualified for England in September, 2004, and was selected to tour Zimbabwe where he averaged 104 in three one-day innings.
Pietersen was selected to play in the one-day series against South Africa early in 2005 and, in the face of unremitting hostility from the home crowds, struck three centuries in five matches.
He was named ahead of Graham Thorpe to play in the first Test of the memorable 2005 Ashes series at Lord's and marked his debut with two confident half-centuries in a losing cause.