I've read raves about this romance from fans of it. I don't look for D/s romances in games myself, but big kudos to Owlcat Games for being able to show the dark eldar properly and consistently, in line with canon. But I would have liked to be able to play with Astarion, he was the one I wanted to play with, and he was the only reason I didn't quit this game. And for his sake, I studied the D/s topic to understand him better, to understand why he needs it, and, accordingly, to accept this option. I put enough emotional and intellectual effort into accepting this D/s option before it finally turned into sadism in the game. And I think the game's authors should also put some effort into making this relationship option possible for acceptance. And as the game is now, it's unacceptable to anyone, neither D/s fans nor other AA fans.
To be fair, it's not unacceptable to *everyone*. I get what you mean, most AA fans don't like it, but while I do find the way the patch 6 kisses to be quite silly in how they're programmed, I appreciate the general narrative that's being presented here, and I've seen a few (not many, definitely a minority in the AA fandom, but a few) people who hold similar opinions.
I chewed on somewhat similar romances that I could recommend because of similarities to Astarion yesterday in my sleep, as they might help someone.
For the D/s crowd, the only other one I can think of that explores that other than Marazhai is Iron Bull from Dragon Age Inquisition. He's a very different character from Astarion though, other than the fact he's bisexual, he's kind of a chaotic-neutral to chaotic-good rugged kind of character. There's no "dark romance" so to speak. Also, he's honestly quite ugly.
For people looking for somewhat similar personalities/vibes, I can think of:
Daeran Arendae from Pathfinder:WOTR. He's a brattish young noble with a tragic backstory who's evil but not in a "mwahahaha murderhobo" way. Reminds me of Lestat, in places. His romance is very focused on the /romance/ part, he's a big romantic. It's not super to my taste, I'm very surprised to see that the overwhelming majority of people think his romance is leagues ahead of Astarion's, but I think it's very shaped by my disinterest in romances for the sake of... romances, if that makes any sense. I do romances to get to know characters better/see more of them, not because of an interest in feeling romantically pursued or seeing a romantic story. I get this is not the most popular or obvious mindset to have, though. Anyways, it's a very popular and HUGELY well-liked romance, I've seen people say it's a romance RPG players need to experience at least once.
Dorian from Dragon Age Inquisition (do keep in mind, he will only romance male characters) has a somewhat similar vibe, I suppose. He's not really evil, but he's snarky and displays a lot of vulnerability and cheekiness with the player.
Fenris from Dragon Age 2 has a very different personality (he's cold and aloof, very uhhh, mysterious) but he's also a morally dubious white haired elf with magic scars given by his previous master on a bloodthirsty revenge quest. You can also do an enemies-to-lovers thing with him, for those interested in that. Can be quite vulnerable.
Zevran from Dragon Age Origins is more similar to Astarion in personality, and he's also a morally dubious charming and flirtatious elf rogue. His backstory with the Crows also bears some similarities. It's a very popular romance, I think.
Finally, I don't think these characters are similar at /all/ (save for being elves) but I've seen a weird overlap between AA fans and Solas fans, so IDK, maybe someone would be interested. Solas is from Dragon Age Inquisition, but do keep in mind he will only romance female elves. I find him to be quite serious and intellectual, he's quite interested in the spirit world and his elven culture/elven ancestors/the ancient elven legacy, so to speak. He's also very morally dubious and complicated once you get to know him, but his motives are compelling and easy to understand.
It's important to keep in mind for those who might care about that that most of these romances, save for Marazhai and arguably Fenris (although it still plays out super similarly in his case), don't have branching paths in the way Astarion does (in the sense that you can go Spawn or Ascended). They're still RPG games where they will react to your different dialogue choices but the general scenes are going to always be the same, as with, say, Karlach (ignoring the epilogue). The other romances with /somewhat/ branching paths I can think of are Alistair and Leliana from Dragon Age Origins, but they're very, very different characters from Astarion.