In her early career Slavica worked as an international fashion model, modelling for a number of leading clients, including the designer Armani. While working on a Formula One promotional event for Armani at the 1982 Italian Grand Prix in Monza, she met Bernie Ecclestone.

From her marriage, Slavica has two daughters, Tamara (1984) and Petra (1988); and four grandchildren.

In November 2008 Slavica filed for divorce after 23 years of marriage. The divorce was granted on 11 March 2009. She topped the Sunday Times’ Rich List in the "richest divorcees" category after she was awarded an estimated £740 million.

Ecclestone was born in Rijeka, PR Croatia, FPR Yugoslavia where her Bosnian Serb parents — Jovo Radić and Ljubica Malić from Maglajani and Riječani, respectively, both villages within the Laktaši municipality, PR Bosnia-Herzegovina — had settled shortly before her birth in search of expanded job opportunities. The family soon moved back to northern Bosnia to her father's village meaning Slavica would spend the majority of her childhood in Maglajani. After her parents divorced when she was only 7 years old, being raised by her mother Ljubica, Slavica was taught to "not do to someone else what you wouldn't want to be done to yourself."