"Jolene" tells the tale of a woman confronting Jolene, a stunningly beautiful woman, who she believes is trying to steal away her man and begging her to "please don't take my man". Throughout the song, the woman implores Jolene "please don't take him just because you can". The song became Parton's second solo number-one single on the country charts after being released as a single in late 1973 (prior to the album's release). It reached the top position in February 1974; it was also a moderate pop hit for her and a minor adult contemporary chart entry, and was released as a single in the UK the following year, where it reached number seven in the UK singles chart.
After performing "Jolene" at Glastonbury festival in 2014, Parton said that the song was inspired by a red-headed woman that Parton felt her husband was spending too much time around when they were newly married. She has also implied that Jolene's name and appearance are based on that of a young fan she met whilst signing autographs.
Post punk band The Sisters of Mercy often covered this song in concert as part of a series of tasteful but goth-"uncool" covers to provoke the audience. It can be heard on their live bootleg Amphetamine-Boeblingen.
The Chilean cumbia compositor Paskual Ramirez made a 'Spanish-translated' cover with cumbia rhythms, partially based on the translation made by Las Chicas del Can for the LP: "Fantasía Vol. 1" (1991) and a techno-cumbia re-arrangement of the cover for the disc Paskual y su Alegría - Internacional (2000). His mate Claudia sang in the 1st version and his daughter Eva sang in the 2000s rearrangement.
A 1994 version by Swedish show group Spirella Girls was named "Brolin, Brolin" and was about Swedish soccer player Tomas Brolin.
Also in 2011, Samuel Larsen performed this song in the finals of Oxygen's reality competition series The Glee Project. Larsen won the competition along with a fellow contender.
It was also performed on the show Glee by Dot Marie Jones who portrays Coach Beiste in the episode "I Kissed a Girl". The episode aired on November 29, 2011.
In 2012, The Little Willies covered the song on their album For the Good Times with Norah Jones on lead vocals.
In 2012, Brandi Carlile covered this song on her Bear Creek tour.
In 2012, Miley Cyrus (Parton's goddaughter) performed a version in a "Backyard Sessions" video found on Cyrus' official website. She also performed the song as part of her Bangerz Tour.
In 2012, Sandra van Nieuwland, a Dutch singer, covered this song for her album And More.
In 2013, Straight No Chaser, an a cappella group from Indiana, covered this song (with featured vocalist Dolly Parton herself) on their 2013 album Under the Influence
In 2013, YouTube user goodlittlebuddy's slowed-down version of "Jolene" rose to internet fame. The song is being played at 33RPM instead of 45RPM, which represents a 25% slow down from the original.