Haymes was born in Buenos Aires, Argentina, in 1918. His mother, whom Haymes predeceased, was Irish-born Marguerite Haymes (1894–1987), a well-known vocal coach and instructor of English descent. His father worked as a rancher and was of English descent. The Haymeses traveled extensively before settling in the United States when Haymes was an infant.

At the age of 17, Haymes moved to Los Angeles where he initially worked as a stunt man and film double. At the age of 19, he moved to New York City where he worked as a vocalist in a number of big bands. On September 3, 1942, Frank Sinatra introduced Haymes on radio as Sinatra’s replacement in the Tommy Dorsey band. Prior to joining Dorsey’s group, Haymes sang with the Harry James orchestra.

From 1944 to 1948, he had his own radio program, The Dick Haymes Show, first on NBC and later on CBS.

In 1945, Haymes co-starred with Jeanne Crain, Dana Andrews and Vivian Blaine in the musical State Fair. He teamed with female vocalist Helen Forrest for many hit duets during World War II, including “Together,” “I’ll Buy That Dream,” and “Long Ago and Far Away”; he sang with Judy Garland on two Decca recordings of songs from the film The Shocking Miss Pilgrim, in which he appeared with Betty Grable.

He paired repeatedly with the Andrews Sisters (Patty, Maxene, and LaVerne) on a dozen or so Decca collaborations, including the Billboard hit “Teresa,” “Great Day,” “My Sin,” and a 1952 rendering of the dramatic ballad “Here in My Heart,” backed by the sisters and Nelson Riddle’s lush strings. His duets with Patty Andrews were also well received, both on Decca vinyl and on radio’s Club Fifteen with the sisters, which he hosted in 1949 and 1950. He also joined Bing Crosby and The Andrews Sisters for 1947 session that produced the Billboard hit “There’s No Business Like Show Business,” as well as “Anything You Can Do (I Can Do Better).” His popular renditions of tender ballads such as “Little White Lies” and “Maybe It’s Because” were recorded with celebrated arranger Gordon Jenkins and his orchestra and chorus.

In 1953, Haymes went to Hawaii (then a territory and, technically, not part of the United States) without first notifying immigration authorities. On returning to the mainland United States, he was nearly deported to Argentina, but won his battle to remain in the United States.

He appeared as unscrupulous doctor Elroy Gantman in a 1974 episode of the TV show Adam-12.

On March 28, 1980, Haymes died from lung cancer in at Cedars-Sinai Medical Center in Los Angeles. He was 61 years old.