Connery- From Russia With Love (hard to pick between this and Goldfinger, but FRWL gets better every time I see it)
Lazenby- OHMSS (admittedly, this being my favorite Lazenby Bond film says literally nothing, but for the record I do really enjoy this one)
Moore- The Spy Who Loved Me (Easily Moore's best Bond film, though Golden Gun has the best of Moore's villains by far)
Dalton- Living Daylights (License to Kill may have far better villains, but overall I enjoy this one more, love both Dalton films though)
Brosnan- Goldeneye (the only of Brosnan's films that I really love, Sean Bean is one of the franchise's best villains)
Craig- Casino Royale (Eva Green is the best Bond girl in the entire franchise, and I doubt that will ever change, Craig is absolutely fantastic in his first outing, and that they managed to make the poker game between Bond and LeChiffre as captivating as they did is impressive as hell)
Casino Royale is my overall favorite, with Goldeneye at a close second