Rosa Klebb (From Russia With Love, 1963)
Hatchet-faced harridan Rosa Klebb is the mastermind behind a plot to assassinate – and humiliate – James Bond with the help of a decoding machine and duped Russian cipher clerk Tatiana Romanova. She's chiefly memorable for her lethal choice of footwear, packing a concealed knife in her sensible shoes. It makes for one of the more hilariously awkward fight scenes in the Bond films, as she hops at Sean Connery while he tries to fend her off with a chair.
David Bowie and Sting turned down the role of microchip tycoon Max Zorin, but Christopher Walken stepped in to play the platinum-blond psycho – a product of Nazi eugenics experiments. A yuppie villain for the Thatcher years, Zorin's scheme involved triggering an earthquake to flood Silicon Valley, giving him a stranglehold on the world microchip market.