"Burn" was written by Taj Jackson, Jonas Jeberg and Mich Hansen, and was produced by Jeberg and Cutfather. It was made available for digital purchase on 17 November 2008. A digital extended play with an additional track and two remixes of "Burn", was released on 24 November. "Burn" is an R&B-dance track, that incorporates electronica influences. Lyrically, it features Mauboy singing to a cheating lover, "Look what you did to me / I need a doctor, cos this is starting to burn!".
Nick Bond of MTV Australia wrote that song is "worthy of Rihanna". Davey Boy of Sputnikmusic compared "Burn" to Mauboy's previous single "Running Back", writing it "is almost as good with its restrained use of electronica combining with a contagious chorus to result in a song which will be just as at home on radio as it is in the clubs." Dung Le of Mediasearch found "Burn" more "catchier" than "Running Back" and noted that its R&B grooves and catchy chorus will set "Jessica up well for a big assault in 2009 and a possible overseas release." "Burn" was awarded an ARIA No. 1 Chart Award for reaching number one on the ARIA Singles Chart. At the 2009 Deadly Awards, "Burn" won 'Single of the Year'. It was nominated for 'Highest Selling Single' at the 2009 ARIA Music Awards, but lost to "Running Back".
In February 2009, "Burn" was removed from most Melbourne contemporary hit radios playlists because of its title and the Victorian bushfires that occurred during the time. Mauboy's manager David Champion said that Mauboy understood and supported the decision, saying: "Jessica is very mindful of the terribly traumatic situation that is occurring in Victoria. She does not want in any way to add to people's distress." Program director of 91. 5 FM added that: "We have removed several songs from our line-up out of respect for the victims caught up in the tragedy. Even though these songs had nothing to do with the bushfires, they were a reflection of it."
"Burn" debuted at number 30 on the ARIA Singles Chart on 1 December 2008. After climbing the chart for seven consecutive weeks, "Burn" peaked at number one on 19 January 2009, and became Mauboy's first number-one single in Australia. It was certified platinum by the Australian Recording Industry Association (ARIA), for selling 70,000 copies.
The music video for "Burn" was directed by Keir McFarlane and shot at the Sydney Botanical Gardens on 21 November 2008. The video begins with Mauboy sitting in the driver's seat of a red ferrari and then moves on to sing and dance in front of a bush. While singing the chorus of the song, Mauboy is seen outdoors with her backup dancers in front of a background of flames. The video then crosses over to club scenes where Mauboy is dancing alongside a bunch of people.