Man, I went on a real deep dive for this stuff after reading 'The Deep' by Rivers Solomon—which isn't a romance but man, the worldbuilding!—and it got me hunting. For mermaid aliens, you've gotta check out 'A Strange and Stubborn Endurance' by Foz Meadows; it's not all underwater, but the aquatic alien societies are breathtakingly different, all about bioluminescent communication and cities built in giant crustacean shells. Then there's 'The Last Hour of Gann' by R. Lee Smith. Okay, hear me out—the aliens aren't classic mermaids, but there's this amphibious species with a fully realized, brutal aquatic-adjacent ecosystem that feels wholly alien. The world is so wet and strange it scratches that itch.
For something more traditionally romantic, Ruby Dixon's 'Ice Planet Barbarians' universe has some spinoffs with water-dwelling aliens, like 'The Alien's Little Sister'. It's lighter, friskier, but the underwater caves and thermal vents are fun. Honestly, the 'unique' part is hard because so many just do Atlantean palaces. I find the ones that truly feel alien focus on non-human senses—like perceiving pressure changes as music, or navigating by tasting mineral runoff.
My shelf is basically a coral reef of weird aquatic sci-fi now.