Sean Connery's Bond seems almost uninterested; he's suave in Thunderball, but it derives from a strange combination of bullying disdain and bored virility. Every woman gives him a second look--but he looks just once, takes a piece, moves on--a super-powered, horn-blaring theme song wailing away in the background, Tom Jones infinitely more excited than Bond himself.
Maybe it's the set of Connery's mouth: I can't tell if he's grimly resolute or vaguely amused--but how could he be both? He has the same look whether he's flying a strapped-on jet-pack, sucking the poison out of a gorgeous girl's foot, spear-gunning SPECTRE henchmen, or winning at the casino. But I don't think it's wooden acting on Connery's part. He simply understands that he's in a comic strip--where everything whirls around the hero while his face remains impassive. It does not move, but waits for the next violent movement. Bond is all instinct; he knows exactly when to apply the proper karate chop, so why fuss about it? He reminds me of Miles Davis, who in performance is attentive but solemn, in complete control of the situation, waiting patiently for his opportunity. Bond's cool is similar, with the added advantage of atomic missles.