I know this may sound a bit obvious but,

'Star Spangled Banner' - Jimi Hendrix.

He was the daddy of making guitars sound different, and although, we may all pay lip service homage to this track, it is difficult to imagine/remember how unusual this track was at the time, he pioneered many sounds that were totally new.

I just know you guys are gonna just hurl when I say this, BUT:

On that DVD of Warren Zevon making his last record, The Wind, Bruce Springsteen comes into the studio, straps on his Fender Esquire, and, with Warren sitting not two feet away, does the most
passionate, heartfelt, soul-stirring, kick-ass solo these ears have just about ever heard. It just goes on and on and on, too - like he doesn't ever want it to stop, cuz when he does, he knows it's over. His last solo for his dear friend, Warren.

But when it IS over, Warren is pretty much speechless. He goes, "Whoah. You really ARE him!" And Bruce leans over his guitar and kisses and hugs his friend.

Word.

Guitarists and guitar solo afficianados everywhere owe it to themselves to witness this one. Even if you think Bruce is pants. This one'll make your ears (and heart) bleed.

I like Frank Zappas solo on What's New In Baltimore ?, the instrumental version on Son Of Cheep Thrills.

Slayers Captor Of Sin is good, it starts with a solo.

Is this unusual, or are there lots of songs that start with guitar solos ?

The best 12 string acoustic playing has got to be Leo Kottke.

If we're talking geetar - Janie's Got A Gun - Aerosmith

Best solo ever - The Kiss by The Cure

I posted Sugarcube earlier in the thread, but come to think of it I think Stockholm Syndrome (track seven on the same album) has an even better solo! I'd say at least the first eleven tracks on I Can Hear The Heart Beating As One are nearly perfect.