The song was released as the album's lead single in Australia on 5 February 2010[1] and in the United Kingdom on 7 March 2010.

Its accompanying music video was directed by Michael Gracey and is heavily inspired by the 1968 science fiction film Barbarella.

In an interview with Digital Spy music editor Nick Levine, Cilmi said, "I guess it will surprise people who thought I was going to make 'Sweet About Me' part two.

"[2] In an interview with BBC News, Cilmi also admitted to borrowing the bassline from Joe Jackson's hit single "Steppin' Out".

Jon O'Brien from Allmusic said that: " The lead single "On a Mission," a gloriously camp retro-fueled anthem, manages to evoke the spirit of Olivia Newton-John's "Xanadu," Toni Basil's "Mickey," and the Bangles' "Walk Like an Egyptian," all in one Hi-NRG three-minute song.

[4] Nick Levine from Digital Spy reviewed the song positively, stating that "it's a proper pop stomper that sounds like something the Pointer Sisters could have had a hit with in 1982.

There are Casio-ish synths on the verses, the bridges take the song into disco territory, and it's got a big, guitar-driven chorus that grabs you on first listen.