Wolff was born in Atlanta. She began her musical training on the trumpet, and as a teenager performed as a soloist with the Atlanta Symphony.
In 1950 she went to study voice at Philadelphia's Academy of Vocal Arts; after singing the lead role in Leonard Bernstein's Trouble in Tahiti for NBC in 1952, she left the stage to start a family.
She made her New York City Opera debut in 1958, and performed there with such artists as Plšcido Domingo and Beverly Sills. She appeared in the world premieres of Gian Carlo Menotti's Labyrinth and Douglas Moore's Carrie Nation.
In the early 1960s, Wolff performed for President John F. Kennedy; in 1975 she performed Verdi's Requiem for Pope Paul VI at the Vatican.
Wolff moved to Lakeland with her family in 1967; she was artist in residence at Florida Southern College from 1981, when she retired from performing, up to her death.