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Zeani was born, Virginia Zahan, in Solovăstru, Transylvania, Romania. She studied first in Bucarest, with famed coloratura soprano Lydia Lipkovskaia, and in Milan, with the great tenor Aureliano Pertile. She made her professional debut in Bologna, as Violetta in La traviata, a role she would sing an estimated 648 times around the world during her career. Her partner that evening was tenor Arrigo Pola (Alfredo), the voice teacher of Luciano Pavarotti.
Her career was first primarily focused in Italy, where she sang at most opera houses, but soon her reputation led to invitations at major opera houses of Europe as well. Violetta was her debut role in London, Vienna, and Paris. She made her debut at La Scala in Milan in 1956, as Cleopatra in Handel 's Giulio Cesare, opposite Nicola Rossi-Lemeni, whom she married shorthly after.
She won considerable success in belcanto roles, such as Lucia di Lammermoor, Gilda in Rigoletto, Elvira in I Puritani, Linda di Chamounix, before turning to more dramatic roles, such as Manon Lescaut, Tosca, Fedora, Adriana Lecouvreur.She also tackled a few Verdi and Wagner roles, such as Lina in Stiffelio, Elsa in Lohengrin. She created the role of Blanche in Dialogues des Carmélites in 1957, at La Scala.
She sang with tenors such as Beniamino Gigli, Ferruccio Tagliavini, Carlo Bergonzi, Alfredo Kraus, Luciano Pavarotti, Plácido Domingo, etc. A warm-voiced singer with an affecting stage presence, she made few commercial recordings, but a number of her live performances exist as bootleg recordings.
Following her retirement from the opera stage in 1983, Zeani remained active as a voice instructor at Indiana University in Bloomington, Indiana, where she and her husband, Nicola Rossi-Lemeni, were both honored as "Distinguished Professors".
After her husband's death in 1991 she taught at IU for many more years before moving to Florida. There she continues to teach, in particular for the Florida Grand Opera Young artist program and the Palm Beach Opera Young artist program. Amongst Zeani's most famous pupils are Marilyn Mims, Susan Patterson, Sylvia McNair, Stephen Mark Brown, Elizabeth Futral, Vivica Genaux, Angela Brown, Mark Nicolson, and Heidi Klassen.