I think this is a really subjective opinion: there are many guitar players that have excellent technique, but I think that what really matters it’s their own style, their personal signature on the music they perform.
From my own point of view, I would definitely have to say that one of my favorite it’s Jimi Hendrix: I was already a big fan when I listened to Blues, a very nice peak into Jimi’s roots, and with it, I understood a little more about his influences. But I became really amazed with Burning Desire, a collection of experimental sessions that, IMO, really expose the unique relation that Jimi established with guitar.