So when she heard about his latest project, a diary called Making a Difference in which each week features an inspirational story and photo, she had no hesitation in helping out, not only contributing 12 stories to the diary but coming to New Zealand to help promote it.
It has been 10 years since the 35-year-old actress was foiled by Bond, when he found the miniature pistol between her legs.
She recalls the audition for Die Another Day, directed by Kiwi Lee Tamahori, when her real-life martial arts skills with nunchucks so impressed Bond actor Pierce Brosnan that he insisted she be cast as the assassin.
Her favourite Bond actor was Roger Moore, because he was so suave and cool.
"To me, he was gorgeous.
"But I do like Pierce Brosnan.''
She is hugely impressed by the Kiwis she has met throughout her professional career, including Mark Staufer, who gave Rachel her first break in TV.
"I can't believe how many talented Kiwis there are all around the world _ all from a country with only 4 million people.''
Her acting career took off after Die Another Day and she now regularly rubs shoulders with some of the big names of the acting world, balanced alongside her work for charities such as the natural cosmetics manufacturer Human Nature, which ploughs all its profits back into helping the poor in the Philippines.
Rachel was recently invited by Hilary Clinton to the White House, as one of the most influential Filipinos contributing around the world.
She is related to British royalty through her grandfather, the late Baron Raymond De Longueuil, who was a second cousin to the Queen.
The baron's mother was Ernestine Maude Bowes-Lyon, the family of the late Queen Mother.
Rachel grew up in London but her mother made sure that she visited the Filipino side of the family every year.
So how does she like her Martinis?
"Shaken, not stirred, of course.''
Making a Difference can be ordered from www.ystories.org for $24.95. It was published to inspire young New Zealanders to make a difference, with sales raising money for Wellington Free Ambulance and Rachel's family charity in the Philippines.