The Adventures of Wiglaf and Mordred: Arthur has got a bad case of this for his little brother Mordred — so much so it tends to get in the way of his evil villainy. His staff often enjoy pointing out the brother complex he claims doesn't exist.
Aisopos: Lenius has this towards his younger brother, Daross. From the moment he entered the agoge, he promised himself he would protect him at any costs. Considering the harsh conditions and Daross's sensitive personality, it made sense that he sent him to Athens back when they tried to help Aesop return from Sparta.
Jamie and Rob in Distillum are pretty much brothers, with Jamie taking the role of the older, protective one (he is older, taller and generally more confident than the shy Rob).
DNA: Sirius is very protective of Orion and the other kids. When Jay kicks Orion to get him out of the mud, which (Rigel had just been trying to drown Orion in), he bites Jay in the leg and looks like he is about to kill him with his powers before Orion stops him. In Segment: Mud, he goes berserk when he sees that Rigel made Lukas cry.
Dominic tends to act this way toward his cheerful, overly optimistic little brother Gregory. Was kind of justified when the comic started because Gregory was infected with a necromantic taint that was slowly killing him, but it was removed early on and now he's perfectly healthy while Dominic is missing a leg.
Played with between Dominic, Gregory, and their older brother Jacob. Jacob spends significant amount of time and parts of major plot-lines trying to maim his little brothers for his own advantage, though he claims there's no emotion involved and it's just part a convenient part of his plans rather than malicious. And yet, he immediately does far, far worse to those who hurt them first.
We're introduced to Elon of Ears for Elves when he's searching for his younger sister Myari after she's run off into the dangerous forest. He gives her a severe talking-to, but has her best interests at heart.
In Chapter 98, Anna offers Gunnthrá a free swimsuit (a bikini naturally) if she'll pose for some pictures, which Anna intends to sell for a fortune. Not willing to let his sister be exploited, her brother Hríd shows up completely out of nowhere with a bag of gold to buy the swimsuit instead.
Michalis: My sisters and I may be foes, but even I agree this would cross a line. I would have no choice but to... break down, like a child.
In Frankie and Stein, Frankie and Adam seem to have this relationship. They haven't really known each other that long, but Adam is very concerned for her, and her current crisis.
GF Serendipity: Stan. Despite being justifiably angry that his brother abandoned him for ten years, he still decides to check on him after hearing he's gone missing and clocks Bill Cipher when he has possessed Ford.
Despite the fact that his sister is sadistic, cruel and rightfully frightens him at times Tarvek does everything in his power to save her after his father uses her in an experiment, since she is his sister. When she dies anyway he still finds himself attached to the clank with her memories and has a difficult time disabling it emotionally even though he thought it would be easy for him since his sister is dead.
Tarvek and Violetta are actually cousins but they are far more like siblings than Tarvek is with his actual sister. He sends her away for her own safety even though it put him in danger and one of the very few things in his life he is proud of is finding her a place where she can be happy. When he thinks she's been killed he goes on a rampage.
Jae Gu of Girls of the Wild's has been raising his siblings since their father's death and mother's abandonment of them. Needless to say, harming them will piss him off really quikcly. When they got sick suddenly, he carried them barefoot to the hospital, leaving footprints of blood by the time he gets there. After finding out they had gotten food poisoning off of tainted sushi someone gave them on purpose, he walked, feet still bleeding, all the way to the person's school and attempted to beat them down with a chair for what they did.
Ellen has shown she's just as willing to stand up for Elliot when he's threatened/hurt as viceversa. In her other life, this trope is more or less how she befriended Tedd. Ellen has more of this that gave Elliot Chronic Hero Syndrome. She's very uninhibited and shows extremeprotectivenesstowardeveryoneclose to her.
Grace's brothers also have some of this in them, though they don't show it nearly as much as Elliot does towards Ellen. Even though Damien scared them shitless, Hedge tried to subvert the orders concerning her as much as he could without being killed.
Adam Summers from Forestdale acts as a pseudo big brother to the rest of his friend group, thrashing any bullies who try to harm them without a moment's hesitation.
Kyle Kendricks also gets a few protective big brother moments with his little sister Racheal. First by giving an atomic wedgie to a younger bully who was harassing her and later watching her back when she's participating in the Forestdale snowball war for the first time.
Hand Jumper: Samin she genuinely cares about Sayeon, doing background checks on anyone who gets close to her and sending someone to keep an eye on her when she joins the Aberrant Corps, despite knowing Sayeon fully intends to arrest her someday (she's far from a model sibling, of course, as she intentionally traumatized Sayeon at a young age to make sure that she wouldn't disobey her).
Equius is extremely protective of his moirail, Nepeta. In fact, this is the first thing that shows us that maybe he's not that bad a guy.
The thought of his twin sister dying is one of the few things that manages to unnerve Dave.
John did not take it well when he found out that Davesprite had broken up with his sister Jade.
Finally, although Bro Srider is shown to be an absolutely crappy parent to Dave, to the point of emotional, physical abuse, even implied CSA, he does slice a meteor in half and give up his rocket board to get Dave safely into the game, and later dies trying to save the kids' session.
No. 1 towards No. 2, veering on Knight Templar Big Brother given that he absolutely flips upon meeting Baekmorae. While not regarding that particular incident, Dune lampshades this trope when discussing No. 1 with Dana.
Sasa, though not related to Naga and Hyena by blood, occasionally displays this, likely due to being the oldest member of the trio.
In Jupiter-Men, Ario treats the twins almost like younger siblings and goes out of his way to talk down some sophomores who planned to pester "the Jupiter-Man kid". He wouldn't hesitate to take a bullet for the twins and refers to their mom as "Aunt Bee" while helping her with groceries. He's also a literal older brother to his younger sister, Jessie. In Episode 25, Arrio even says Quintin is like a brother to him. The minute that Quintin reveals that he has superpowers and is putting his life on the line to protect people, Arrio goes from running away from the supervillain to running at him and trying to lure the villain away from Quintin and Jackie.
Viktor is violently protective of Ivy. To the extent that every boyfriend she wrangles is pounded to the point of a full body cast. This is particularly noticeable when you contrast it with how he reacts to others, which usually tops off at Vague Irritation at best.
Rocky, for all his personality quirks and questionable morality, has a bit of this for his younger cousin Calvin, better known as Freckle (who he was raised with and who he more or less treats like his younger brother). It's implied that [[spoiler: Freckle got into some kind of trouble when he was younger, probably due to his habit of occasionally going berserk, and that Rocky took the blame for it, which is further implied to be the reason Rocky got kicked out of his Aunt Nina's house, so that Freckle could go on to live a semi-normal life.
In an Even Evil Has Loved Ones variant, Nicodeme Savoy is two years older than his sister, best friend, and partner in crime Serafine. Despite her being more than capable of taking care of herself, he's still protective of her, though the sentiment is clearly mutual and the two generally look out for each other. In the animated short based on the comic, the otherwise-bloodthirsty Nico gets a clear Pet the Dog moment when, upon realizing a stick of lit dynamite is about to go off near where Serafine is standing, immediately throws himself over her to shield her from the blast.
In MYth, Hades is a heartbreaking example. He destroyed the bond he had with his little brother Zeus in an attempt to make him strong enough to be king of gods.
Roy develops this for Elan, though it (understandably) takes a while, and he still denies it. Roy actually did have a little brother, (key word here being did), and Elan has a living twin brother but has been shown explicitly thinking of Roy as his brother instead.
Roy has a literal little sister, for whom he feels the same protective need (despite crazy moralitydifferences). Proof? He went to rescue her from villains, knowing fully well that it was a trap all along.
Larima of Pacificators fame thinks she's protecting her younger sister Taffe, but, really, it's the other way around. (Oh, and it annoys Taffe.) Later chapters shows that Larima really is a protective big sister; Taffe just doesn't realize it, because much of Larima's actions take place behind Taffe's back.
Pixie and Brutus: Brutus takes his role as Pixie's "new big brother" very seriously. If anything could possibly hurt or upset her, he's on-guard against it.
In Sakana, Taros gets really angry whenever someone threatens or talks bad about his little brother Jiro, and is always there to care for him and cheer him up when he has a problem.
Vinnie, the werewolf from Skins. He looks out for the irresponsible happy-go-lucky vampire, Rabbit and acts as a kind of substitute big brother. He's known Rabbit since they were orphaned in the last occult war.
Onni has this towards his younger sister Tuuri and his younger cousin Lalli, who for all intents and purposes might as well be second younger sibling to him. He later gets dragged into visiting a strange dreamspace location by budding mage Reynir. When the location turns out to not be as deserted as they thought, Onni's first reflex is to protect Reynir from whatever threat the place's resident may represent.
Emil has this towards Lalli, despite Lalli actually having more field experience than him at just about the same age. There are two factors explaining it. One is that Lalli has an unknown disorder that makes people who don't know him that well assume he is less able to take care of himself in a dangerous situation than he actually is. Second, Emil doesn't believe in magic and thinks the "mage" on Lalli's resume is just a fancy title. The end result is that if Lalli exposes himself to the giant monster attacking their night train in just the clothes in which he's been sleeping, Emil's thoughts are less "the train guards could probably use his assistance" and more "I need to get him out of here before he gets himself killed".
Manly Man from NSFW Comix is this towards his sister, or at least, her love life as he literally kicks men he finds unworthy of her out of her life. The only man he ever liked was one he molded into a virtual clone of himself, and that led to the sister kicking him out of her life, because dating someone that much like her brother was too incestuous for her tastes.
Maria from Rain (2010) is very protective of her brother Rudy as the latter is often mocked for being openly gay. Especially by the school's bully Todd. She is often there to intimidate them as for them to not harm her younger brother.
In Sticky Dilly Buns, Dillon and Jerzy briefly go into what Dillon later calls "mother hen mode" when Andy presents a rather disconcerting gift to Ruby during a dinner date.
Hyun slowly develops this with the two kids he rescues as he starts to worry more and more about their safety.
Hyuk's first action after every major development is to make sure his sister is okay.
Kenny towards his brother Jake in Weak Hero. Originally a member of the Manwol Gang, he attempts to retire and tells Jake it's because he wants to focus solely on his football career- however, a different scene beforehand revealed that Kenny was actually doing it because the Manwol were attempting to recruit Jake, and Kenny didn't want his brother to get involved in gang activities. He does this even knowing that the Manwol won't take kindly to him leaving- and, indeed, they end up permanently crippling him and ruining his future career as a footballer.
Yoona used to be this to her twin brother in Welcome to Room #305. She was tall tomboy who would beat up boys who would bully her sensitive brother. As adults she is a Big Sister Bully though.
Aiden in Winters In Lavelle has this towards his little sister, Kari. It's even been said by Keshii that the main reason why he dislikes Ashton is because he can tell that Ashton has a thing for his sister.
morality differences). Proof? He went to rescue her from villains, knowing fully well that it was a trap all along.
