My top 5 songs:
1. Live and Let Die - I can't explain why, but this is my favorite
2. Goldfinger - probably the quintessential Bond song, the one that began the trend (From Russia With Love only had the song during the end credits)
3. A View to a Kill - the movie left a lot to be desired, but Duran Duran hit this one out of the park
4. Skyfall - harkens back to the classic Bond song feel
5. You Only Live Twice - there's just something really soothing about this
If you include the orchestral intros, the opening for On Her Majesty's Secret Service is one of John Barry's best works. The use of it throughout the score was done perfectly.
Honorable mention: Thunderball, You Know My Name (Casino Royale), GoldenEye, The World is Not Enough