Hundreds of stars and invited guests milled around the pristine foyer for the red carpet opening of the new 14-screen venue, billed as the biggest all-digital cinema in Europe.
Veteran movie critic Barry Norman was among the crowd, along with Rolling Stones survivor Bill Wyman, All Saint Melanie Blatt and TV fashion guru Mary Portas.
The 700 guests enjoyed a champagne and canape reception before choosing from three films – James Cameron's box office-breaking sci-fi epic Avatar, and exclusive screenings of horror remake The Wolfman or all-star romantic comedy Valentine's Day.
They were each given glasses for trailers of some of the upcoming, high profile films to be shot in the resurgent 3D format.
Vue hopes the venue, which already has five 3D projectors and can be converted to hold more, will quickly rival the West End as London's top cinema destination. The all-digital set-up means films can be changed around quickly, with 38 different titles playing in the opening week.
It includes two giant Vue Xtreme screens, each the size of four double decker buses, and three 'SCENE' screens for over-18s who are happy to pay extra for a more luxurious experience.
Tim Richards, CEO of Vue Entertainment said: "We're incredibly excited about opening our flagship cinema at this prestigious location in Westfield London that attracts over 23 million visitors a year.
"Vue Westfield is set to become London's first choice premier film destination, offering a range of brand new cinema experiences under one roof. 2009 has been a record year for cinema here in the UK, smashing the magic £1 billion box office milestone, and 2010/11 looks set also to set break new records with a wide mix of exciting and entertaining movies, together with more non-film content including live music, sport and comedy.
"With such a wide choice of entertainment, we expect this cinema to be a massive hit for local visitors and from the wider surrounding areas."
Vue has pledged to continue operating its cinema in the nearby West 12 centre, which will screen mostly Bollywood and independent films.