Pauline was born in 1976 and grew up in Khayelitsha, Cape Town. She sang in local choirs from an early age and was first exposed to the world of opera during a high school outing to Don Giovanni. Pauline enrolled at the University of Cape Town College of Music to study a Performers Diploma in Music, performing in the chorus of several opera productions.

Pauline joined Dimpho Di Kopane in 2000 where she was selected to perform the lead role in Bizet's opera Carmen. Replacing the current lead with only three weeks to prepare this new role, Pauline rose to the occasion and went on to achieve tremendous international acclaim.

Pauline plays the Virgin Mary in Yiimimangaliso The Mysteries, Lucy in Ibali looTsotsi The Beggar's Opera, and a thief in IKumkanikazi yeKhephu The Snow Queen.

Pauline co-wrote and translated the screenplay for U-Carmen eKhayelitsha, and plays Carmen in the film.
Replacing the current lead with only three weeks to prepare the role, Malefane rose to the occasion and went on to achieve tremendous international acclaim, being described in The Observer, London as "the Carmen by which others should be measured".