Born in Beglej, Bulgaria, Dimitrova studied at the Sofia Conservatory and made her debut in Sofia as Abigaille in Nabucco. She later studied at La Scala's opera school. In 1972, she won the Treviso competition, launching her career in earnest: that year she appeared at the Teatro Regio di Parma as Amelia in Un ballo in maschera with Jos_ Carerras.

Dimitrova debuted at the Vienna State Opera in 1978, and sang regularly at the Arena di Verona starting in 1980. She made her U.S. debut in 1981, singing the role of Elvira in Verdi's Ernani at the Dallas Opera, and made her New York debut in 1983 with the Opera Orchestra of New York. She first appeared at the Metropolitan Opera in 1987.

Her most frequently performed roles includes Abigaille, Gioconda, Turandot, and Norma.