Pete Duel was born on February 24, 1940, in Rochester, New York, to Dr. Ellsworth and Lillian Deuel, and was the eldest of three children, including a younger brother Geoffrey and a sister Pamela.
He attended Penfield High School, where he was an active member of the school community, working on the yearbook staff, campaigning for student government, and joining the National Thespians Society.
After high school, Deuel moved to New York, where he landed a role in a touring production of the comedy Take Her, She's Mine. He and his mother then drove across the country to Hollywood, California, in 1963, with only a tent to house them each night.
In Hollywood, Deuel found work in television, initially landing the starring role of Dave Willis in the romantic comedy Love on a Rooftop. Although the show earned good ratings, ABC decided not to bring it back after its first season, leading Deuel to wish to move from sitcoms to more serious roles. Around 1970, he also changed his name, dropping the "r" from Peter and the first "e" from "Deuel".
In 1970, Deuel was cast as the outlaw Hannibal Heyes, alias Joshua Smith, opposite Ben Murphy, in the light-hearted western Alias Smith and Jones, about the exploits of two outlaws trying to earn an amnesty. During the hiatus between the first and second seasons, he starred in the television production of Percy MacKaye's 1908 play, The Scarecrow.
Deuel became involved in politics during the 1968 presidential election, campaigning for Eugene McCarthy, in opposition to the Vietnam War. He attended the 1968 Democratic National Convention in Chicago and witnessed the violence that erupted.
In the early hours of December 31, 1971, Deuel died at his Hollywood Hills home of a self-inflicted gunshot wound to the head, with his girlfriend Dianne Ray discovering his body. Ray later told police the two had watched Deuel's series Alias Smith and Jones the previous evening, and she had gone to sleep in another room while Deuel stayed up.
According to police, Deuel's friends and family said he was depressed about his drinking problem, having been arrested and pleaded guilty to a DUI accident that injured two people the previous June. Deuel's death was later ruled a suicide.
Deuel's funeral was held at the Self-Realization Fellowship Temple on January 2, 1972, in Pacific Palisades, with an estimated 1,000 friends and fans attending. His body was later flown to Penfield, New York, where he was buried in Oakwood Cemetery.
After his death, his role in Alias Smith and Jones was taken over by Roger Davis, and the series was eventually cancelled in 1973 due to the loss of Deuel and the difficulty of fans to accept Davis as his replacement.