Head began writing songs as a child, and by the mid-1960s he had a London-based recording contract. He had limited success, until asked by Tim Rice and Andrew Lloyd Webber to play Judas Iscariot on the original concept album version of Jesus Christ Superstar; at the time, he had been appearing in the West End production of the musical Hair. With the Trinidad Singers, the song "Superstar" peaked at No. 14 on the Billboard Hot 100 chart in 1971.

He made his film debut in The Family Way (1966), which featured Hayley Mills, Hywel Bennett and John Mills in the leading roles. Head won a leading role in the Oscar-nominated film Sunday Bloody Sunday (1971), alongside Peter Finch and Glenda Jackson. Despite these successes, he received little public attention in the next ten years (except for his single release, "Say It Ain't So, Joe" in 1975, which has been covered by The Who's lead vocalist, Roger Daltrey, among others, including The Hollies). "Never Even Thought" has been covered by both Colin Blunstone and Cliff Richard.

Murray Head married Susan Ellis Jones in 1972; they divorced in 1992. He has two daughters: Katherine and Sophie. Sophie sometimes sings with her father, for Example on songs such as "Seras-tu là?" on the album Tête à tête and "Make It Easy" from the Emotions album.

In 1973, he appeared in a radio drama, The Fourth Tower of Inverness. In 1979, Head appeared in the miniseries Prince Regent and the final episode of the ITV program Return of the Saint.

Head reappeared in the spotlight in 1984 as the American on the concept album for the musical Chess. The song "One Night in Bangkok" featured Head on lead vocals, affecting a New York accent. It became the last significant Broadway/West End number to be a hit single on American and German radio until "No Matter What" by Boyzone in 1996. "One Night in Bangkok" was a success in both Europe and North America. Head performed the role of world chess champion Frederick "Freddie" Trumper in the London West End stage production of Chess that premiered on 14 May 1986. The show ran in London until 8 April 1989; during its run, Head departed with vocal strain.

After that, Head had little recording success in the UK or the United States. This fact would later be underscored in a radio segment featured on The Kevin and Bean Show on KROQ-FM in Los Angeles, in which the hosts would phone Head in the morning to find out "What's Up with Murray Head?" Fluent in French, he has released a number of albums in that language. A duet with Marie Carmen, "Une femme un homme", was released in 1993 and was a hit in French-speaking Canada.

In 1999, Head co-wrote the screenplay to Les Enfants du Siècle.

Murray Head was born in London to Seafield Laurence Stewart Murray Head (1919 – 22 March 2009) and Helen Shingler (born 1919). Head's father was a documentary filmmaker and a founder of Verity Films. Head's mother played Mme Maigret alongside Rupert Davies in the BBC 1960s television adaptation of the Maigret novels written by Georges Simenon. Head's younger brother Anthony Head is also an actor, best known for playing Rupert Giles in the TV series Buffy the Vampire Slayer.

He has appeared on television in the UK on The Bill, Casualty, North Square and Judge John Deed. He also played an Artist, and love interest of Gina Ward, called Jack Hollins on ITV's Heartbeat from 2005–06. On 15 March 2010 he appeared in the BBC drama Doctors playing a pop singer, Pete Perry, trying to make a comeback, in which Head sang Robert Johnson's "Love in Vain". In Canada, he was part of the cast of the 2002 television mini-series Music-Hall, which played on the Radio-Canada network. In 2011 he appeared in the first episode of the series Vera (episode "Hidden Depths") as Peter Calvert.