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This is a tough topic because of how the sound of a guitar has evolved throughout music. I personally feel that its Hendrix and Eddie Van Halen. Hendrix made his guitar sing and EVH is phenomenal. Check out Respect the Wind from the Twister soundtrack for EVH's best solo IMHO.
I see that quite a few of you use Limewire. Try a search on these guitarists and then tell me what you think. These three are the real deal. Also, if you're going to throw Hendrix into the mix you should add a few of his contemporaries. Page and Blackmore come to mind. Then there's the prodigy Ozzy found who died very young in a plane crash that might have been the best I've ever seen live (I've seen both Gilmore from Floyd and Page with Zeppelin live), Randy Rhodes.
In No Particular order