The range, which includes drinks such as Hot Winter Punch and Malibu Ginger Snaps, will be launched in bars and other on-trade outlet in the run-up to Christmas.
Dixon will host an "ultimate girls' night out" at Studio Valbonne, London, on 12 November, as part of the marketing campaign.
She will perform to a private concert of 200 competition winners.
Winners on the night will be able to sample the brand’s new cocktails and make use of make-up artists and stylists at the event.
The main prize on offer is for one winner and three friends to sip cocktails with Dixon prior to her performance.
The brand is launching four cocktails: Vanilla Ice, Ginger Snaps, Caribbean Lights and Hot Winter Punch, which will be available later this month.
Patrick Venning, head of marketing for Malibu at Pernod Ricard UK, said: "Teaming up with Alesha Dixon will speak directly to our core target audience of 22 to 25-year-old females.
"This campaign will help reinforce our message that Malibu is instrumental in ‘setting the stage’ for a fun night out – whether that’s having a drink while getting ready at a friend’s house, or sampling a cocktail in a local bar or pub before moving on to a club."
Hopefuls can enter the competition via Malibu’s Facebook page from today (15 October), at www.facebook.com/MalibuUk