DuVall is also co-founder, lead singer, guitarist and lyricist for Comes with the Fall.
DuVall's music career started in the early 1980s Atlanta hardcore punk scene. He first performed with Awareness Void of Chaos.
In 1983, DuVall helped found the controversial Atlanta-based hardcore punk band Neon Christ, contributing guitars and lyrics to the band's albums. Neon Christ had strong ties to hardcore luminaries Corrosion of Conformity and Bl'ast. With a couple of short East Coast tours and two albums, the politically-pointed band started gaining popularity. The band used its popularity to support many charitable causes including working to free Fela Anikulapo Kuti.
The band disbanded in 1986, reuniting for a one-time show featuring the original members on December 24, 2004. Currently, the members along with Joseph Stalin are said to be filming a documentary, which concluded with a February 2, 2008 show at Lawrenceville, Georgia's punk haunt The Treehouse.
After Neon Christ originally broke up, DuVall was briefly the second guitarist in the popular Northern California hardcore punk band Bl'ast, contributing a small bit of writing to their second album, It's In My Blood, released on the hardcore punk–alternative label SST Records, founded by Greg Ginn of hardcore punk band Black Flag. DuVall did not, however, stay with the band long enough to record on the album.
DuVall spent the late 1980s with a Jimi Hendrix-inspired band, No Walls. They released one album. He also spent the late 1980s in college earning a degree in Philosophy.
In the late 90s, DuVall founded the band Madfly with Nico Constantine, Bevan Davies and Jeffery Blount. He served as guitarist, singer and songwriter. Their efforts included two albums, Get the Silver and White Hot In The Black, both released on Duvall's own label DVL Recordings, the latter distributed nationally by Mercury Records/PolyGram.
DuVall befriended musician Jerry Cantrell in 2000. Quickly becoming Cantrell's go-to man, DuVall has performed with Cantrell on tour and multiple shows, including Cantrell's band Alice in Chains, which DuVall is currently fronting in place of Layne Staley, who died of a drug overdose on April 5, 2002.
In 2007, Alice in Chains, fronted by DuVall, began touring with Velvet Revolver and Kill Hannah. The ReEvolution tour was in two parts. The first took in many European cities and the Eastern United States. The second part, also referred to as "The Libertad Tour", is primarily a cross-country tour that spread into three cities in Canada. For the first time in 15 years Alice In Chains toured Australia as second headliner under Nine Inch Nails on the Soundwave Festival. Personally, it was Duvall's first visit to Australia. It had since been advertised on the official Alice in Chains website that the band – now with Duvall officially noted as lead singer – was working on new material with an album, now known as Black Gives Way to Blue, released on September 29,