How High the Moon performed by Les Paul and Mary Ford on the vocals.
Although the thread title does specify rock, I think most fans of that genre will acknowledge the significant influences and innovations of Les Paul. Plus, I'll admit that the song is a personal favorite from the era of my childhood when my tastes were being formed.
In fine print, I'll also wedge in a mention for Grady Martin's great guitar riff (albeit not an intro but in the middle) on Don't Worry by Marty Robbins. I don't necessarily buy the well-traveled story that the fuzz/distortion was accidental though. YMMV.
We now return the thread to the young people and rockers. This oldtimer is off to dreamland soon. :-)
*Tip of the hat*
The sky’s the limit, and this thread could have gone on for day if I didn’t specify rock, but there are so many greats:
Chet Atkins
Glenn Campbell
Brent Mason
Pat Methany
Al DiMeola
Segovia
Larry Carlton
Allan Holdsworth
I also would have mentioned Robert White of The Funk Brothers, and his intro to My Girl.
Gene Krupa in Sing Sing Sing...absolutely primal. And I am not an old guy.