Inspired by all the recent retrospectives in the Star Trek community, I am compiling a list of guest actors in roles other than what they were famous for. I will start with the first season of The Next Generation.
Long before he became Quark on Deep Space Nine, instead of a Ferengi, Armin Shimerman was just a talking box containing Deanna Troi's bonding gifts in the TNG episode "Haven".
After being Ben Childress in the TOS episode "Mudd's Women", Gene Dynarski came to serve Starfleet in the 24th century in the TNG episode "11001001".
Before he became Admiral Forrest in Star Trek: Enterprise, the first Star Trek alien that Vaughn Armstrong played was a Klingon in the TNG episode "Heart of Glory". He was a tough guy. It took more than one phaser blasts to bring him down. We also get to see the Klingon death howl for the first time.
After appearing in the movies with the original cast, Merritt Butrick and Judson Scott butted heads in the episode "Symbiosis". Well, they shocked each other with their hands.
Before Henry Darrow became Chakotay's father, he had the distinction of playing the first Vulcan male in the 24th century, in the TNG episode "Conspiracy". He also attempted a neck pinch on Riker. I don't think it was very effective as Riker did not even pass out.
Before donning any Cardassian make-up prosthetic, Marc Alaimo was one of two 24th century Romulans first seen by Starfleet, in the TNG episode "The Neutral Zone". BTW The way outposts on both sides were destroyed is the first prelude to the Borg.