Born Vivian Stapleton, the cherry-blonde-haired Blaine appeared on local stages as early as 1924 and was a touring singer with dance bands starting in 1937. In 1942, her agent and soon-to-be husband Manny Franks got her signed to a contract with Twentieth Century-Fox, and she relocated to Hollywood, sharing top billing with Laurel and Hardy in Jitterbugs (1943) and starring in Greenwich Village (1944) and State Fair (1945), among other films.

Following her Fox years, Blaine returned to the stage, making her Broadway debut in the Frank Loesser musical Guys and Dolls in 1950. Her character Adelaide has been engaged to inveterate gambler Nathan Detroit for 14 years, a condition which, according to her song "Adelaide's Lament", can foster physical illness as well as chronic heartbreak. After the show's 1200-performance run on Broadway, in which she starred opposite Sam Levene as Nathan Detroit and Robert Alda as fellow gambler Sky Masterson, she reprised the role in London's West End in 1953, and then on film in 1955, with Frank Sinatra playing Nathan and Marlon Brando in Sky's role.

Blaine also appeared on the Broadway stage in A Hat Full of Rain, Say Darling, and Enter Laughing, as well as participating in the touring companies of many musicals, such as Zorba. As she reached age 50, her television career took off, with a semi-regular role on Mary Hartman, Mary Hartman and guest roles on shows like Fantasy Island and The Love Boat.

Blaine's first marriage, to Franks, lasted from 1945 to 1956. She then married Milton Rackmil, president of Universal Studios and Decca Records, in 1959, and recorded several albums prior to their 1961 divorce. In 1973, Blaine married Stuart Clark. She retired from show business in 1984, and died of congestive heart failure in 1995 at age 74.