Amity Blight as of "Covention", where she reveals the full extent of her Inferiority Superiority Complex and how badly it affects her. Mae Whitman especially sells it with her voice-acting. It only increases in "Lost in Language", where we get to see what her older siblings are like and learn from her personal diary entries that she actually feels awful about coming off as mean toward other people but is trapped into doing so by her pathological need to never display weakness. On top of all that, she’s expected by her own parents, mostly her mother, to be the best she can be. Thankfully she gets better.
King. Although nowhere near as mean as Amity, he counts as a milder version of the trope. Sure, he's a rude, snarky, self-centered creature with a Napoleon Complex but in "The Intruder", he opens up to Luz about how he doesn't have many friends and feels unloved, and his attempts to be taken seriously all stem from these feelings of inadequacy. The fact that he looks to be on the verge of crying will make you want to reach into your screen and cuddle the poor little guy.
And of course we have Eda, Unscrupulous Hero par excellence who is also suffering, possibly in a fatal way, from a curse placed upon her when she was younger, and Lilith, Eda's sister who still loves her despite their opposing viewpoints and who genuinely thinks that bringing her in to the Emperor's Coven will be "helping" her. To make things worse, in “Agony Of A Witch” it turns out that Lilith is one who cursed her in the first place because she was jealous of her magic superiority.
The Golden Guard/Hunter is a loyal enforcer for Belos who is perfectly okay with threatening to torture Luz and Eda and killing the selkidomus. It turns out he's a powerless witch who believes he owes everything to Belos -his uncle- and is regularly abused by him, instilling Hunter with the belief that he must prove himself worthy of being loved. It gets worse as Hunter is shown to be a decent guy whenever he defies Belos and is actually an Expendable Clone the emperor has no love for.
Those fears ended up being very real, considering that in the last episode she makes a Heroic Sacrifice (although, unlike her previous attempts, this one was merely an instinctive and impulsive act to protect a loved one, as she was hoping to save herself at the same time.)
Her life prior the events of the series wasn’t much better, either. Not only is hard enough for her to be neurodivergent (Dana confirmed Luz suffers from ADHD), but her father died from a terminal illness when she was very young, and her love for fantasy stories (more specifically of The Good Witch Azura series) came from the fact he gifted her a copy of the first book before his death, so she relied on them to cope with her grief. The issue was that her hyperactive imagination and recklessness made her a social pariah to her peers for years, as she was even looked down upon by other kids’ parents. The reason why the plot of the series kickstarted in the first place was because she wanted to prove her mother and by extension her school that her creativity and weirdness could be used in a productive way with her book report, only for it to horribly backfire and Camila being pressured into sending Luz in a “camp reality check” in a well-meaning, but misguided attempt to protect her from bullying. It’s no wonder that by the time the series even starts, she has a very low opinion towards humans (except her mother), so much so that she literally jumps to the opportunity of making a life for herself in the Demon Realm, even though it’s not her “Isekai fantasy” she has always dreamed of.
Luz’s mother, Camila is one herself. It’s mentioned that the loss of her husband made her fall in a depressive state, and she tried her best to support her daughter and protect her from other grownups’s scorn, doing so all on her own as she loved her husband too much to ever start dating again, even after his death. But, Luz’s reckless stunt with her book report forced her to Luz in said “normal camp” when she could no longer resist the pressure from society expectations. In “Thanks To Them”, it’s revealed that she was bullied in her youth for being a nerd (although of Sci-fi stories, rather than fantasy like her daughter), and in “For The Future” she admits that her biggest mistake of her life was to try to suppress Luz’s authentic self out of a misguided attempt to protect from the same pain she had endured.
Heavily implied with the Collector of all people. True, they are a godlike entity from the stars who uses Reality Warp abilities to "play" with other people mostly without realizing the harm they can cause and then "collect" them when they no longer want to play. However it's hinted that our Collector, much like Luz, Eda, and King, is an outcast of their own kind, since unlike other Collectors, they don't want to kill whoever they find irritating to them and they actually get some attachment from whoever is part of their "collection", just like an actual kid gets attached to their favorite toy, and their true deepest wish might be to find a true friend that would never leave them and would play with them forever. This is eventually confirmed in “Watching And Dreaming”, where their backstory (being cast out by their sibling, being caught in the crossfire of the Titan War, and being wrongly trapped in another dimension by King’s father) and motives are explained. Finally, once they do understand the concept of death through Luz’s Heroic Sacrifice, they’re desperate to not let Eda, King and the Hexsquad kids get killed by Belos.
