Oh man, one of my favorite topics :

Alright, here goes:
Close to the Edge and
America Yes; Steve Howe is an absolute master of all things guitar.
Sister Andrea (the live version from Between Nothingness and Eternity) Mahavishnu Orchestra; John McLaughlin's picking and fretwork is just ridiculous, especially for the era.
Buckethead Colonel Claypool's Bucket of Bernie Brains; Just a fantastic solo, incredibly crisp while pulling off some awesome shit
Bulls On Parade Rage Against the Machine; Tom Morello at his inventive best
Sway The Rolling Stones; Mick Taylor was a fantastic, pretty underappreciated guitarist
Plume and
Starla The Smashing Pumpkins; Starla is pretty much the 90s Freebird in my opinion. But better. So much better. Holy guitar noise, batman. I loves me some Corgan solos.
Ebin Sublime; I miss Brad Nowell
Dazed and Confused (the How the West Was Won live version) Led Zeppelin; Basically just Jimmy Page tearing shit up for like 15 minutes.
Jambi Tool; I love distorted talkbox. Actually speaking of,
Do You Feel Like I Do (Frampton Comes Alive version, obv.) Peter Frampton; man, I hate Peter Frampton. This song is great though.
Tax Free (Live at Winterland) Jimi Hendrix; So good. SOOOO GOOD.
Cult of Personality Living Colour; Vernon Reid is a supreme badass.
White Room Cream; My favorite Clapton solo.
All I can think of off the top of my head.