Daniels is a singer, guitarist, and fiddler, who began writing and performing in the 1950s. In 1964, Daniels co-wrote "It Hurts Me" (a song which Elvis Presley recorded) with Joy Byers. He worked as a Nashville session musician, often for producer Bob Johnston, including playing electric bass on three Bob Dylan albums during 1969 and 1970, and on recordings by Leonard Cohen. Daniels recorded his first solo album, Charlie Daniels, in 1971 (see 1971 in country music). He produced the 1969 album by The Youngbloods, Elephant Mountain and played the violin on "Darkness, Darkness". His first hit, the novelty song "Uneasy Rider", was from his 1973 second album, Honey in the Rock, and reached No.9 on the Billboard Hot 100.
Daniels played fiddle on many of The Marshall Tucker Band's early albums: "A New Life", "Where We All Belong", "Searchin' For a Rainbow", "Long Hard Ride" and "Carolina Dreams". Daniels can be heard on the live portion of the "Where We All Belong" album, recorded in Milwaukee, WI on July 11, 1974. In 1974, Daniels organized the first in a series of Volunteer Jam concerts based in or around Nashville, Tennessee, often playing with members of Barefoot Jerry. Except for a three-year gap in the late 1980s, these jams have continued ever since. In 1975, he had a top 30 hit as leader of the Charlie Daniels Band with the Southern rock self-identification anthem "The South's Gonna Do It Again". "Long Haired Country Boy" was a minor hit in that year. Daniels played fiddle on Hank Williams, Jr.'s 1975 album Hank Williams, Jr. and Friends.
Daniels won the Grammy Award for Best Country Vocal Performance in 1979 for "The Devil Went Down to Georgia", which reached No. 3 on the Hot 100 in September 1979. The following year, "Devil" became a major crossover success on rock radio stations after its inclusion on the soundtrack for the hit movie Urban Cowboy. Daniels appeared in the movie. The song is by far Daniels' greatest success, still receiving regular airplay on U.S. classic rock and country stations, and is well-known even among audiences who eschew country music in general. A hard rock/heavy metal cover version of the song was included in the video game Guitar Hero III: Legends of Rock as the final guitar battle against the last boss (Lou, the devil). Daniels has openly stated his opposition to the metal cover and the devil winning occasionally in the game.
Subsequent Daniels pop hits included "In America" (#11 in 1980), "The Legend of Wooley Swamp" (#31 in 1980), and "Still in Saigon" (#22 in 1982). In 1980, Daniels participated in the country music concept album, The Legend of Jesse James. In the late 1980s and 1990s, several of Daniels' albums and singles were hits on the Country charts and the music continues to receive airplay on country stations today. Daniels released several Gospel and Christian records. In 1999 he made a guest vocal appearance on his song "All Night Long" with Montgomery Gentry (Eddie Montgomery and Troy Gentry) for their debut album, "Tattoos and Scars," which was a commercial success. Daniels' distinctive speaking voice was used in Frank Wildhorn's 1999 musical, The Civil War. He is featured in the Prologue and "In Great Deeds."
Daniels was inducted into the North Carolina Music Hall of Fame in 1999.
In 2000, he composed and performed the score for the feature film Across the Line starring Brad Johnson. He guest starred as himself in an episode of King of the Hill titled “The Bluegrass is Always Greener”, which aired on February 24, 2002. In 2005, he made a cameo appearance along with Larry the Cable Guy, Kid Rock, and Hank Williams, Jr. in Gretchen Wilson's music video for the song "All Jacked Up". In 2006, he appeared with Little Richard, Bootsy Collins, and other musicians as the backup band for Williams' opening sequence to Monday Night Football.
On October 18, 2005, Daniels was honored as a BMI Icon at the 53rd annual BMI Country Awards. Throughout his career, Daniels' songwriting has garnered 6 BMI Country Awards; the first award was won in 1976 for "The South's Gonna Do It Again". In November 2007, Daniels was invited by Martina McBride to become a member of the Grand Ole Opry. He was inducted by Marty Stuart and Connie Smith during the January 19, 2008, edition of the Opry at the Ryman Auditorium.