"I was a giggling mess and I don't know how I got through it - it was very difficult to do," she said. "He was so lovely and supportive, because I was on my first day. It was a bit like 'hello, how are you? let's snog and do it over and over again' so it was fine."
But while Gemma was honored to play a Bond girl, she admitted she preferred her lead role in Tess Of The D'Urbervilles.
Wearing a show-stopping purple frock, the starlet - who has also starred in Three And Out and St Trinian's in the past year - said she felt privileged to have played a variety of roles so far in her career.
"Actually Tess is my favourite role," she said on the red carpet. "I've played such different roles all the way through, and that's how I want it to be. And to play a Bond girl... I never thought I'd play a Bond girl. So it's kind of 'wow'."
Quantum Of Solace is in UK cinemas on Friday