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.