"From Russia, With Love," is my favorite. Looking back on it during my first read, I didn't think that it would be, since it seems like a while before Bond enters the story. But the beginning description of SMERSH operations and the realism and accuracy of it all is very exciting. I would argue that it could even be considered historical, if Fleming got it right, which I'm sure he did.
But I enjoyed all of the novels. Except that I have never found a copy of "The Spy Who Loved Me," so I have never read it, nor really wish to. I had heard that it was Fleming's least favorite, and taken first person from the woman's point of view. What does everyone else think of it? Should I try to hunt down a copy?
Yes. It's a different approach to a James Bond story, but if you are a fan of Fleming's other work, I believe you will find it rewarding (perhaps even moreso than some of his other novels).