If we stick to just rock n’ roll, and not going into rock, I guess I’d say “Heartbreak Hotel” by Elvis. I’m not much of a true rock n’ roll listener, but that song seems to represent rock n’ roll to me.
But of course, overall, the greatest rock n’ roll song (not defining) for me is “(I Can’t Get No) Satisfaction” by the Rolling Stones. One of the greatest songs ever.