GTA3 and VC- (Those intro songs were some of the best stuff I've heard in any recent game.)
Legacy of Kain: Soul Reaver (So good it set the mood of the entire game, everytime I heard that beat, it made me want revenge just as much as Raziel.)
Bandit Kings of Ancient China(NES)- That was one awesome, funky, asian beat, I never even liked that game, I just turn it on to hear that one intro song.
Shadowlands(PC)- This is another old game I keep around just to hear the intro, I swear anyone out there that likes funky techno should download this game and listen to how good the intro music is. It's a great mix of classical fantasy style music and hardcore techno.
Tom Sawyer(NES)- Yeah the game sucks, but the opening song is absolutely beautiful.
Equinox(SNES)- The intro was wonderful and the whole soundtrack was, the thing about this game was it's background music was as subtle as it was beautiful. It would come and go at any random time, sometimes there would be hours of no music, then boom you get a new weird song, wonderful soundtrack, wonderful game, yet 3rd sequel.
Super Ninja Boy(SNES)- Not only did the actual music rock, the actual intro was kickass too, I loved the weird noises those little dudes made.
Shadows of the Empire- The people in charge of the music for this game should be very proud of themselves. With most other SW's games they just rehash the same old music from the original trilogy, but this game totally had it's own soundtrack that totally had the feel of the SW's universe. The intro theme, which was also Dash Rendar's theme was amazing to hear, it was like Total Recall with the SW's vibe, excellent stuff. I wish more games could create totally original SW's music. *cough* Jedi Knight *cough*
Chrono Trigger- Great intro music, the funny thing is though, it kinda reminded me of soap opera music.
Granstream Saga- Another great fantasy tune, it also had some of the most enchanting sound effects I've ever heard in a game.
Last but not least, Xenogears! The intro for this just blew me away, Xenogears was one of the first rpgs I seriously sat down and really got into, man was the music in this great, but I haven't ever really played an rpg with bad music, that's the one genre that never fails me in that department.