1. Casino Royale
3. The Spy Who Loved Me
5. From Russia With Love
If I had to fill out a top ten:
6. The Living Daylights (great Bond flick with the most underrated Bond, but had the two worst villains in the series)
7. Quantum of Solace (the Bond film that deconstructed all the tropes that make up a Bond film, the best Bond sequel/movie plot continuation, and a severely underrated movie IMO)
8. Goldfinger (introduced the world to the Bond standard of guns, gadgets, and gals, I just haven't seen it in a long time and the opening act was a little slow from what I remember) barely miss the top five.
Octopussy and Tomorrow Never Dies round out the top ten.
Let's throw License to Kill for a top eleven Bond films list.