Sean Connery in Dr No, when he first utters the immortal line "Bond, James Bond"; a rough caricature of the latest 007, Daniel Craig; and a generic non-specific-actor Bond.
And some Bond villains...
Donald Pleasance as Blofeld (the definitive interpretation of the character, in my opinion) in You Only Live Twice; and Mads Mikkelsen as La Chiffre in Casino Royale.