Lucy Moore, a 20-year old student from Portsmouth, scooped 22% of the vote in a poll hosted on the Ann Summers website.
The vote was publicised via a television campaign that set out to find "the sexiest face in the UK".
Twelve women finalists then starred in an ad shown on ITV2 in November, after being chosen from a total of 4,000 entrants.
Lingerie and sex toys retailer Ann Summers will use images of Moore in its store windows from 19 January, while the student will also star on the cover of the Ann Summers Valentine's Day catalogue.
Moore will also give her lingerie-buying tips throughout the catalogue and on the brand's website.
Ann Summers says the appointment of a "real woman" as the face of its campaign is one of many firsts for the brand since it was relaunched in early 2011.
The television campaign highlighting the competition was the first time the brand had embarked on television activity, while it also recently launched a new store concept at its flagship store in Westfield Stratford City.
Ann Summers is also busy striking a number of commercial partnerships, including one with Shop Direct and another with relationship counselling charity Relate, which will see the launch of a "sex census".
Follow Matthew Chapman at @mattchapmanUK