Might depend on what you consider 'rock' & whether 6/8 would sneak in as 3/4- but how about The Animals, House of the Rising Sun. 1964.
Or Moody Blues - Go Now.
Beatles - You've Got to Hide Your Love Away. 1964.
The trouble with the 60's is rock hadn't quite been invented yet, so the answer might turn out to be Hendrix.