James Bond star Daniel Craig, playing the spy for a third time, was the first of the stars to arrive at the Royal Albert Hall for the royal premiere.
“It’s incredible,” said Daniel Craig.
“This is my third premiere and this is the biggest and the best.”
Skyfall is the 23rd official Bond film and marks 50 years of the franchise.
Large crowds of people had turned out to cheer the stars on the red carpet, which stretched along the streets around the venue in Kensington, west London.
The Prince of Wales and the Duchess of Cornwall attended the screening on Tuesday night, along with stars Dame Judi Dench, Javier Bardem and the film’s director Sam Mendes.
James Bond received the royal seal of approval earlier this year at the Olympics opening ceremony when Daniel Craig’s character appeared in a short film alongside the Queen.
Daniel Craig said he was “incredibly proud” to be playing the hero created by Ian Fleming, who first appeared on the big screen in Dr No in 1962.
“It was the 50th year so we had try and celebrate that,” he said.
“Sam and I are huge Bond fans and we wanted to make the best Bond movie we could, and he’s done a tremendous job.”
Proceeds from the royal gala are going to charities that help members of Britain’s intelligence services.
Skyfall sees spy chief M (Judi Dench) battling a crisis with roots in her past, and Javier Bardem playing a villain bent on revenge.
Javier Bardem said: “Sam Mendes has done something very challenging which is to mix the flavor of the classic Bond movies with something more modern.”
Sam Mendes said: “The weirdest thing is that about two weeks ago I was still finishing the movie with about three other people in a dark room – so the big shock is coming out and finding people about to see the movie.”
Other stars on the red carpet included Ralph Fiennes, who plays a senior government official, Bond girls Naomie Harris and Berenice Marlohe, and Ben Whishaw as the new Q.
Ben Whishaw said: “I’m so thrilled to be a part of this phenomenon.”
Naomie Harris, who plays British agent Eve, said she tried to avoid watching the performances of previous Bond girls as she prepared for the role.
“I didn’t want to be influenced by that. What was much more useful to me was interviewing a former MI6 agent who came along and answered all our questions about what it was like to be a real agent.”
Berenice Marlohe, who plays the mysterious Severine, said on the red carpet: “We filmed the movie a long time ago but suddenly it brings back all the memories, and I feel very moved to be here.”
Barbara Broccoli, who co-produces the Bond films with Michael G. Wilson, said Skyfall was “classic Bond but with a contemporary feel”.
She added: “We wanted to make a film for the 50th anniversary for the fans and we wanted to make the best Bond ever – we tried real hard so I hope the audiences like at as much as we enjoyed making it.”
Skyfall has been praised by critics, with some indeed hailing it as the ultimate Bond adventure.
The Independent’s Geoffrey McNab said: “If not a full-blown triumph, this is certainly one of the best Bonds in recent memory.”
The Times’ Kate Muir called it “a great British bulldog of a movie”.
All eyes will be on the box office after the film opens on Friday to see if Skyfall can top Daniel Craig’s other outings as the secret agent.
2008’s Quantum of Solace made $586.1 million worldwide, while Casino Royale (2006) made $594.2 million.
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