Opening sequence. Bond skies off the mountain, the film goes silent except for the sound of wind, Bond unfurls a Union Jack parachute, and the piano for "Nobody Does It Better" begins. Goosebumps. Every time.
"To be the man, you gotta beat demands." -- The Lovely Mrs. Tracker
This is a bit offbeat, but I'm not a big James Bond afficionado:
My favourite scene is from A View To A Kill. Toward the end of the movie, there's a mine that's collapsing, and while workers are escaping, Christopher Walken's character picks up an uzi, says, "Oh look, there's still some clips left", and begins to mow down workers running for safety from the mine.
The entire parkour sequence in Casino Royale was incredible, but my favorite part of it was when Bond and the guy he's chasing jump from the cranes. The soundtrack even has an "oh, shit!" moment in it.
I liked how in Die Another Day, they pull a shocking swerve (I mean, a real one) and have Bond not escape the bad guys at the end of the opening sequence. Instead, he's tortured in North Korea for 15 months. Too bad the film went downhill from there.
I liked the black-and-white sequence from Casino Royale-- both the fight, and the cold-blooded way in which Bond kills Dryden. "Well, you needn't worry. The second is..." *BANG* "Yes. Considerably."
I liked the fight on the train in From Russia With Love, and the fight on the plane (and hanging from the plane on a cargo net) in The Living Daylights.
"If I die in here, I'll kill him!" --Urdnot Wrex, Mass Effect
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Pretty much everything in From Russia With Love is a highlight. The shootout at the gypsy camp is particularly exciting, but the helicopter chasing down Bond takes the cake for edge of your seat moments.
As previously mentioned, the climax to the ski chase in The Spy Who Loved Me is quite possibly the most spectacular stunt I've ever seen (and I've watched an absurd amount of action films).
And finally, Dalton's entire performance in Licence to Kill. If I could pick a particular moment, it's where he offs the goon that killed his buddy Sharkey. "Compliments of Sharkey," Bond says, before shooting the guy in the gut with a harpoon gun. Vicious.