The Whitecoat, a Super Hero from The Descendants rocks a white stetson so nice that people think it's somehow part of his powers. They would be right, because he's got a vid screen with a heads up display under the brim!
The Minion in Project Million looks too conspicuous with her mask, so Hagan makes her switch it to a top hat with Mickey Mouse stuffed through the middle. It's still big enough to cover her entire head.
Yahtzee Croshaw of Zero Punctuation wears a distinctive trilby. In ZP's simplistic art style, it distinguishes him from other characters. In real life he said he wears it less since it started to get him recognised.
The League of S.T.E.A.M.'s zombie manservant, Zed, wears a fez. Baron von Fogel and Coyote wear Dashingly Dapper Derbies. Sir Conrad, Jasper Mooney, Professor Jager and Mrs. Potts wear top hats, Ellie Copperbottom wears a mini-tophat, and Thaddeus wears a boater.
In episode 26, The Music Video Show wears a skull tuque after several episodes of various plain looking hats.
The Double Agent wears a nice fedora. At first he abandoned it but it received alot of love which then lead to him wearing the fedora again.
In the early chapters of Dive Quest, Muschio comes across several hats that don't really do much for him. Then someone suggests he put on an animal skull, which actually looks pretty respectable. Then, one poster urges him to put another hat on top of it, which he does... then, while he's at it, he puts on the other hat, and then he starts throwing everything he can think of onto his head in sarcastic deference to the voices in his head, including the crystal ball through which they manifest and keep voicing their collective obsession with hats...
Mad? I'm not mad! I'm just following your fantastic fashion advice!
YOU WANT HEADGEAR? I'LL SHOW YOU HEADGEAR
TELL ME WHAT THE VIEW IS LIKE FROM UP THERE
...and then his sidekick walks in on him with no idea what he's doing. ("quick! put her on your head too!") Muschio stammers something about something or something or other, then foists the mess on her, tells her to make a better hat out of it and runs.
asdfmovie 4 has the following exchange between a sarcastic guy and a top-hatted guy:
"Nice hat." "Thanks!" "I was being sarcastic." "Well, I stole your face!"
If the Emperor Had a Text-to-Speech Device plays with this. While Decius' popehat is rather nice, more or less everyone in-universe seems to agree it absolutely sucks, with the Emperor getting in constant jabs towards it. The rest of the Ecclesiarchy seems to be the only ones who appreciate it, and they themselves wear similar ones, or in one case the closest they could find (a garbage bin with an Aquila symbol).
Homestar Runner: Homestar has his signature red and dark blue propeller cap. Coach Z wears a blue and purple baseball cap and Homsar wears a yellow and orange bowler hat (which, oddly enough, floats up and down as he talks).
Many of the Cheat Commandos wear a variety of hats and headgear, from Gunhaver's brown Stetson hat to Firebert's black beanie.