Honor Blackman, Goldfinger
The iconic character from 1964's Goldfinger Pussy Galore was played by Honor Blackman. She quit her job on The Avengers to appear in the Bond film, and the rest really is history. What set her apart from previous Bond Girls was that she had experience in Judo.
A Doctor Who Regular
Blackman's last couple film roles included 2012's Cockneys vs Zombies and a stint on the sitcom You, Me, and Them, where she played a self-described "selfish" character she wasn't fond of. She also appeared on Doctor Who as Professor Lasky for a time.