The programme attrached a 36.4% share of the audience in the 9pm slot, the business reality show's best ratings to date, according to unofficial overnight figures.
McQueen, who will earn £100,000 a year in his new job, has been given the task of forming a venture with Amshold, the holding group of Sir Alan Sugar, as part of a real life challenge to develop the new business and sell advertising space.
He said: "Sir Alan has bought a new business doing digital advertising and signage. I'll be running the sales teams with one of his colleagues. It's just what I wanted to do -- start on something fresh and exciting."
McQueen won the fourth and most popular series yet of 'The Apprentice' after a tense final head-to-head with rival Claire Young.
His final task in the series was to launch a new aftershave brand aimed at men, with the help of London-based ad agency DraftFCB.
The task involved designing the product at a concept stage, creating the fragrance, deciding on a name, and creating an ad campaign.
McQueen's team did not want to produce a flowery metrosexual scent, and instead opted for a product straight out of the 1970s.
The team came up with 'Roulette', a musky aftershave with "animal tones", backed by a Bond-inspired ad featuring a male and female couple enjoying a sexually charged moment in a casino setting.
McQueen was not initially one of the favourites to win, especially after it was revealed in the penultimate episode that he had lied about the length of time he had spent at university, but he won Sir Alan Sugar over with old-school decency and his tireless work ethic.
He also scored points with Sugar for revealing he supported Premier League football club Tottenham Hotspur -- the team Sugar chaired from 1991 to 2001.
As Sugar said: "That tells me a lot about you if you support Tottenham."
Audiences had peaked at more than 8.1m for last week's penultimate episode, which pulled in an average audience of 7.5m viewers.