Other cast members on the red carpet included Naomie Harris, Christoph Waltz, Ben Whishaw, Ralph Fiennes, Andrew Scott, Dave Bautista and "Bond girls" Lea Seydoux and Monica Bellucci.
Bellucci said it was a "great pleasure" to be part of the "amazing tradition" of Bond films.
"It's magic," she said. "It's incredible how James Bond represents so much, not just in England actually, but all over the world."
Scott, who plays a new character called Denbigh, said that the franchise had lasted so well because it kept "reinventing" itself.
The Sherlock star added: "The storyline in this movie is about surveillance and how we're watched constantly. There's a lot of prescient subject matter in the recent Bond films."
Spectre is the first Bond film to open in cinemas on the same day as its premiere.
Mendes said he was delighted that the public were also getting to see the film. " I love the idea that cinemas around the country will be full tonight at the same time as we are doing the royal premiere."
Tim Masters, entertainment correspondent on the red carpet
"It's just fantastic to see everybody out tonight," said Daniel Craig as he arrived on the Spectre red carpet that snaked further than the eye could see around the Royal Albert Hall.
Hundreds of fans - some of whom had queued since Saturday - lined the route in the hope of a photo with Craig. He didn't disappoint them.
As several thousand guests surged into the famous domed venue, huge speakers pumped out Bond themes past and present, as clips from Spectre played out on giant screens.
Famous faces on the carpet included Dames Shirley Bassey and Joan Collins, Hobbit star Martin Freeman, musician Will.i.am and former Bond girl Maryam D'Abo from The Living Daylights.
For two hours the whole event was telecast around the world - just as cinema audiences prepared to watch the film for the first time.
When it comes to world premieres, nobody does it better than 007.
The 24th official entry in the franchise sees Bond battling a criminal syndicate led by Franz Oberhauser, played by Waltz.
Spectre is the third Bond film chosen for the Royal Film Performance since its inception in 1946. It follows previous premieres for Die Another Day (2002) and Skyfall (2012).
Early reviews have been positive, with some critics awarding the film five stars.
Speaking to the BBC last week, Craig said he had not made any decisions about whether he would carry on playing 007.
The actor, on his fourth outing as the superspy, had told Time Out magazine that he would "rather slash [his] wrists" than make a fifth Bond film.
But he told the BBC's Lizo Mzimba: "I'm quite straightforward and I say things when I feel it and then I change my mind. I'm just like everybody else."
Speaking to the BBC on the red carpet, producer Barbara Broccoli said: "I'm pretty determined to keep him!"
Spectre was shot at Pinewood Studios and filmed on location in London, Mexico City, Rome and Tangier and Erfoud, in Morocco.
The shadowy organisation Spectre - which was previously an acronym for the Special Executive for Counter-Intelligence, Terrorism, Revenge and Extortion - last made an appearance in 1971's Diamonds Are Forever, with Sean Connery as Bond.
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