She studied at the academy for theatre, film, radio and television in Belgrade. Started her career as a student with a major role as Koštana in a same name play in a National Theatre in Belgrade. There she met Vuk Vučo, a theatre critic whom she later married.
For a role in Goya - oder Der arge Weg der Erkenntnis in 1971 (as Olivera Katarina), she was awarded at festivals in Moscow and Venice. Her major success was in Aleksandar Petrović's I Even Met Happy Gypsies, where she played a gipsy singer named Lenče. Film was nominated for the 1968 Best Foreign Language Film Oscar, for a Palme d'Or (Golden Palm) at the 1967 Cannes Film Festival, and for Best Foreign-Language Foreign Film at the 1969 Golden Globes. It won the FIPRESCI Grand Prize of the Jury at the 1967 Cannes Film Festival. Olivera closed this festival with a concert together with Nana Mouskouri and Dionne Warwick.
She also had a very prominent singing career. She recorded in Serbian language, as well as in Russian, Greek, Romani, Indonesian. She sang traditional Serbian folk songs and Gypsy/Romani songs. In famous Paris Olympia she held 72 consecutive concerts.
Most recently Olivera sang a couple of songs for Marina Abramović's Balkan Erotic Epic. After almost 20 years Olivera is filming again. She plays a goddess in 2007 Uroš Stojanović's film Čarlston za Ognjenku.
She has one son Mane with late husband Miladin šakić. Mane is a painter and lives in Madrid.