Tower of God is an undisputed king of this Trope. Manipulating the Functional Magic of their world known as Shinsoo, allows for a person who become skilled enough with it to become immortal. Since the entire cast and everyone in the the story setting can use Shinsoo, almost all of them are immortal and either are already or soon will be older than they look. A prime example is Anak Zahard who has a body of what seems like a child and is 300 years old. They need to be immortal as well, since their ultimate goal is to reach the top of the Tower that makes up their world and just reaching floor 134note The highest anyone has ever gotten takes 500 years.
Pompey the half-elf is approximately sixteen both mentally and physically; chronologically, he's forty-three, and complains about being called "kid" when it's revealed that he's taking orders from a (human) 21-year old.
Vaarsuvius has two elf children, aged twenty-six, who look and act like small kids and are currently in kindergarten. Both of these are the result of long elflifespans.
Redcloak still looks like a goblin teenager thanks to the Crimson Mantle despite being over fifty (which, for a goblin, is beyond venerable age).
Vinci, of Vinci and Arty, is often mistaken for a child, in spite of being well into adulthood.
Miho of Megatokyo has stated outright that she's older than she looks (about seventeen), though Largo thinks she's ancient. She also refers to a twenty-three year old as "young man" and used to run around with Yuki's mother, Meimi, which pushes her estimated age closer to forty.
Mr. Raven of El Goonish Shive looks fifty-ish, but he's old enough to have taught a current student's mother (herself about forty). At one point, we see him unconscious, and he actually looks younger, implying he has some sort of illusion spell going to make himself look older. Oh, and he's an elf.
Grace is 18. Not all that implausible, but this has caused some in-story surprise when people found out that she's the oldest person among the main cast.
Nina Delacroix of Eerie Cuties looks and acts like the comic's Token Mini-Moe, but she's the same age (14) as her friends and in high school.
Angela from Queen of Wands and Punch an' Pie. She doesn't seem to mind it much, because hey, ordering off the kid's menu is cheaper and you get to color on the placemats.
Torg and Riff of Sluggy Freelance had been old enough to drink for multiple years (They had been giving each other beers for Christmas) at the start of the comic in 1997. Their comic makes note of major holidays, making Comic Book Time and real time correspond to a rough degree. But despite the fact that those two should be close to 40 years old now, neither they (nor anyone else in the strip) has noticeably aged.
Sera from Serenity Rose is extremely short, and the art for the comic is fairly age-ambiguous, to the point that the artist has on at least one occasion included a disclaimer stating she's in College.
Jones of Gunnerkrigg Court looks like she is around thirty. She has always looked like that. Always. She is actually billions of years old and no more human than a rock is.
Homestuck: Dave's Bro looks to be in his early to mid twenties, and the age gap isn't too wide between him and Dave, in reality he's as old as Rose's Mom as a Paradox clone sent to earth on a meteor, he arrived at the same time she did making him in his thirties-forties.
Precocious: Tiffany in this request strip showing the kids as teenagers.
Dina from Dumbing of Age; college-aged, but about half the size of her classmates and lacking in social skills. Lampshaded when Raidah and her friends think she's a child, and later after she makes friends with Riley.
Amber: Dina, I think she's like twelve. Dina: I have been deceived! Riley: Wait, you're not twelve? Dina: I see no answer to that which would not tarnish my dignity.
Magic users in Evon age slower than normal people. Evon looks like a twelve-year old (allegedly) but is actually in her mid-20s.
Nearly everyone in Oz in Namesake. The spell placed on Oz prevented the inhabitants from aging, meaning only those who really wanted to age did so. Ozma in particular appears very young, in her younger teens, despite being however old she really is. In a horrifying twist on the trope the Dorothies don't appear to age physically, but die of old age anyway, to Ozma's despair.
Spinnerette looks like a teenager but she's actually a grad student in her mid- to late twenties. In contrast to "Evil Spinerette" who looks considerably older than the 16 years she turns out to be.