Really bad at their jobs:
Iron Fist/Power Man’s “Hero For Hire” company where they never got paid.
Daredevil’s Law Firm where Foggy works for free and they never get paid.
Homeless people whose job is unpaid superheroism:
Bucky Barnes, the original Bucky, who is basically an orphan who was adopted by some army guys.
Samuel Wilson, The Falcon, who was a reformed pimp and drug dealer who was living on an abandoned island learning to talk to falcons when Captain America found him.
Most of the X-Men except Angel and Xavier, as revealed in many comics and the films, they were usually abandoned by their families and homeless for being mutants.
Shang Chi, no idea how he eats but apparently his weapons are homemade. Somehow walks the streets of New York barefoot, probably not by choice.
The Question and Ralph Digby the Elongated man, whose job is apparently free detective work.
Cloak and Dagger possibly work at a homeless shelter or live there, it’s hard to tell.
Homeless people with irregular work:
Bruce Banner, the Hulk, somehow make tons of money doing government jobs once every few years and spends the rest of the time wandering around getting hunted by them.
Heroes with jobs but bad pay:
Captain America, Steve Rogers, is officially in the Army but apparently not pulling Captain’s salary, although in several issues his “Captain” title is real. In several issues, he usually takes shifts watching the Avengers mansion as a part-time job. He’s also left the army on several occasions to be a comic book artist or school teacher.
Peter Parker, Spiderman, was getting ripped off for his photos for the Daily Bugle for years and usually would repeatedly say his inability to get a full time job prevented him from marrying Mary Jane or completing college.
Hector Ayala, the original White Tiger, lost his job (dishwashing) because of his drug addiction and tried to go back to college.
Wonder Woman’s original employment in WW2 was nurse then secretary to Steve Rogers, and her side job was secretary of the Justice League.
Live a rich life with no discernible income:
Dr. Strange has huge house and servant in Manhattan, probably inherited from the Ancient One, but neither had any kind of job. Known to be absolutely broke from origin issue from his old medical career. Dr. Fate also seems to have a cool lair, cool stuff, and no job.
Oliver Queen, the Green Arrow: seems to be losing/regaining his fortune every other issue.
The Fantastic Four: Reed sells stuff, I think, and apparently they own the entire Baxter Building. The other three members apparently contribute nothing.
Lost their job because of their powers:
Green Lanterns immediately do green lantern stuff full time the second they get the ring and never go back to work. Hal Jordan apparently is so cool that Pieface and his girlfriend both left the airplane company they all worked for.
Ted Grant, Wildcat, whose boxing skills are so good they’re a superpower and prevent him from making money with it in the ring.
Had good jobs that gave them powers and then never worked again:
Hourman: doctor.
Flash: scientist.
Hal Jordan: Test pilot.
Ben Grimm: Test Pilot. (Astronaut?)
Mooches from other dimensions/universes with no Earth money always trying to crash on your couch and eat your food:
Thor
Hercules (at least he has the class to sometimes look for a job)
Silver Surfer
Green Lanterns besides Hal Jordan.
The entire Legion of Super Heroes