"White Unicorn" was one of four songs originally recorded by Wolfmother for the band's self-titled debut EP in 2004, initially under the title "The White Unicorn". It was later re-recorded for the group's self-titled full-length debut the following year and released as the second single from the album on 26 February 2006. The song was backed with "Love Train" and music videos for "Dimension" and "Mind's Eye", all of which had been recently released on the EP "Dimensions". The single debuted on the Australian Singles Chart at its peak position of number 33, remaining in the top 50 for three weeks running. Outside of Australia, it was the band's first track to register on the US "Billboard" Mainstream Rock chart, debuting at number 37, before spending a total of 12 weeks on the chart and peaking at number 29.