Lug from Oxventure Wyrdwood - everyone he spends time with (including the people he leads through the Wyrdwood are smaller than him so he has to look down all the time and everything is built for people smaller than him so he has to like scrunch down to fit into things and I doubt he has enough room in his hovel as he calls it.
Dob from Oxventure - he's six foot four or six foot five and his best friend is five foot three while Corazón is like five foot five and I doubt Prudence is taller than Dob so he's also typically looking down, especially including most of the people the guild interacts with are smaller than him humans. He's also very flexible and bending into all different sorta shapes and I don't think he's worrying about his posture, if he's sitting or laying down he's thinking about what's most comfortable not what it's gonna do to his back.
(Sidenote: I feel like it makes sense to give it to Egbert too but I think all the like stand up straight posture stuff was drilled into him at Le Dragon D'or and it's just embedded in him now)
Edvard Lumiere from Oxventure in the Dark (a lot of Oxventure I know but that's what I'm focused on right now) - no matter how tall you think he is, he is absolutely always hunching over his work bench to work on his innoventions and other projects. I imagine he also likes making himself small for comfort (not in angsty way but you can view it that way if you want, I mean more like a cat curling up in a ball)
Lilith Capellinaga - like Edvard, but moreso, I know she likes to curl up, especially with a good book, and make herself as small as possible, especially considering how much stealth she does. She also reads a lot and it's not a stretch to say she usually has her head down in a book and that could mess up her back as well.
(Another Sidenote: Zillah is also a possibility, but I lean towards no with her)
Silas from Oxventure Deadlands - I just know that man's tall and that he doesn't like being around people so he scrunches himself up in the corner, especially when his teammates take up so much space (monhuns I love you), and that he doesn't actually care that much about his posture.
Zee from the Total Drama Reboot - similar to other folks on the list, he's very tall and most people and stuff are smaller than him so he has to bend down to be near them and fit in frame with them. He's also a chill soda stoner guy so he is absolutely not worrying about his posture and he's just being comfy, dude.
Harold from the original Total Drama run - his body is similar to Zee's as a tall and lanky guy so he has a lot of the same issues, but he's also a geek so he's gonna be reading comics and playing his video games and it's not a stretch that he'd be hunching over to get closer to them.
(I kinda wanna say Jasmine from the Pahkitew Island season of Total Drama because she's my favorite girl from the whole original run of the show but words aren't working for me when I try to form the argument for her right now, or an argument for DJ, really, but also I can see his mom absolutely not letting him slouch in the first place so maybe there's not an argument for him.)