Paluzzi is best known as the villainess, Fiona Volpe, in Thunderball (1965). She had auditioned for the part of the lead Bond girl, Dominetta "Domino" Petacchi, but producers cast Claudine Auger, changing the Domino character from an Italian to a Frenchwoman and renaming her Dominique Derval. Initially crestfallen when informed she did not get the part, Paluzzi rejoiced when told her consolatory prize was the part of Volpe, which she said was "more fun to play". Paluzzi later claimed being a Bond girl was a double-edged sword. In the documentary Bond Girls Are Forever, Paluzzi expressed amazement at the level of fame, publicity, and recognition she received from Thunderball; but as a result of being in such an outlandish film, she felt she was taken less seriously as an Actress when returning to the Italian film industry.