When he was four, Charlie and his mother relocated from San Antonio, Texas to Austin—where clubs such as the Armadillo World Headquarters, Soap Creek Saloon, the Split Rail and Antone's exposed him to popular music.

[2] Under the moniker Little Charlie, he played about 16 dates with the Joe Ely Band in June 1982, after guitarist Jesse Taylor broke some bones in his hand.

[4] Jon Pareles of the New York Times described him as "a teen idol singing David Bowie-style rock during the years he was promoted by MTV".

While he was still in his late teens, Sexton became a popular session player—recording with artists such as Ronnie Wood, Keith Richards, Don Henley, Jimmy Barnes and Bob Dylan.

Sexton later contributed songs to various motion picture soundtracks, including True Romance and Air America—and made a cameo fronting a bar band in Thelma & Louise.

[citation needed] Sexton had previously played with Dylan during a pair of Austin, Texas, concerts in 1991 and 1996, and on some demos recorded in 1983.

Sexton and Colin Linden subsequently shared lead guitar duties for the band from July and into early August.

[15] Sexton continued working with other artists; in 2001, he produced Double Trouble's Been a Long Time, and Jimmie Vaughan's album Do You Get the Blues?

[16] Sexton has produced numerous other works, including Edie Brickell's Volcano (2003), Jon Dee Graham's Great Battle (2004), Shannon McNally's Geronimo (2005), and Los Super Seven's Heard It on the X (2005).

[19] Sexton performed the Leonard Cohen song "Hallelujah" with Justin Timberlake and Matt Morris at the Hope for Haiti Now benefit concert and telethon for earthquake relief In 2010.

[21] Charlie and Will Sexton made a rare appearance as a duo opening for Roky Erickson and Okkervil River at Austin's Paramount Theatre on April 24, 2010.

Sexton was also the guest performer for Conan O'Brien's Legally Prohibited from Being Funny on Television Tour stop in Austin on May 14, 2010.

)[25] In 2018, Sexton appeared in the documentary film Carmine Street Guitars and played Townes Van Zandt in the movie Blaze.

[citation needed] Sexton appeared with Chuck Prophet during the latter's 2019 European tour, covering selections from the Rolling Stones' Some Girls album.

[citation needed] In January 2022, the Arc Angels reunited to play four shows in Texas, with Eric Holden replacing Tommy Shannon on bass.