Written by band members Andrew Stockdale, Chris Ross and Myles Heskett, it was produced by Dave Sardy for the group's self-titled debut album in 2005.

[8] In contrast, Pitchfork's Cory D. Byrom claimed that "Its opening bars recall Led Zeppelin's gentler side with clean-strummed guitar chords and Stockdale putting on his best Robert Plant".

[14] According to Steven Gottlieb of VideoStatic, "Most of the camera angles emanate from behind the band to convey just how big these guys are down under, while various color effects give the clip a slight psychedelic feel".

Writing for the website PopMatters, Adrian Begrand claimed that it "emerges as the clear winner on the entire disc, neatly marrying the hippy-dippy sentiment of Robert Plant and the monstrous chords of Tony Iommi before briefly returning to the acid rock sounds of Hawkwind again".

[19] At the end of 2005, Australian radio station Triple J included "White Unicorn" at number 84 on its Hottest 100 list, the lowest position of the six Wolfmother tracks featured.