The superspy's former flames were overshadowed on the Royal Albert Hall red carpet by Bond's current leading ladies Naomie Harris and Berenice Marlohe, who stunned in a red Vivienne Westwood ball gown.
British actress Harris wore a daring sheer black Marios Schwab dress with a blue sequinned body suit underneath.
Craig was in good spirits as he chatted to event MC David Walliams, telling the British comedian he felt confident his new film was one of the best in the 007 franchise.
He said, "Both (director) Sam (Mendes) and I are huge Bond fans and we just wanted to do the best job."
And he only had great things to say about new Bond villain Javier Bardem.
Craig added, "He's a joy to work with; he's one of the best actors there is... He's up there with the best (villains)."
The James Bond star also got the chance to speak with the premiere's top guests, Prince Charles and his wife Camilla, just before the film began.
Dame Judi Dench and Ralph Fiennes were also on the red carpet for the launch.
Fiennes confessed to being a Bond fan since he was a teenager, adding, "I was thrilled to be a part of the film", while Dench was full of praise for Craig, stating, "He's totally Bond."
Newlywed Holly Valance and her husband Nick Candy, Minnie Driver, Kelly Brook, Tamara Ecclestone and British film couple Sam Taylor-Wood and Aaron Johnson were also among the celebrity guests keen to see the new Bond film.