Daniel Craig was the first of the film's stars to arrive at the screening at the Royal Albert Hall in central London on Tuesday, where he was joined by co-stars Judi Dench, Javier Bardem and Naomie Harris.
Skyfall is the 23rd official Bond film, and Craig's third outing as the suave superspy. Harris is Bond girl Eve, a field agent racked by self-doubt, Dench plays spy chief M, battling a crisis with roots in her past, and Bardem plays Raoul Silva, a Bond villain bent on revenge.
Bardem said he was drawn to the role of Bond bad guy after seeing Jaws, the steel-toothed henchman in 1979's Moonraker.
With some critics hailing the Sam Mendes-directed Skyfall as one of the best Bond films of the half-a-century-old franchise, Bardem said the series' appeal showed that "they have been doing something really right, starting with the actors who have played Bond. They have all brought their own flavour to it."
Craig, dressed in a black Tom Ford suit, appeared to share a laugh with Prince Charles and his wife Camilla ahead of the premiere. Also on hand were Ben Whishaw, who plays Q, and Berenice Marlohe, who plays Bond girl Severine, as well as Olympic cycling champion Victoria Pendleton and model Kelly Brook.
Skyfall opens in Britain on Friday and in the U.S. on Nov. 9. Proceeds from Tuesday's royal gala are going to charities that help members of Britain's intelligence services.