Well the first comic character I read was Captain America, Captain America #1. What was the first comic you read and who was the main character?
A very old He-Man comic an old guy sold to me for the equivalent of a dime. (My peso to dollar conversion may not be spot on but I'm sure it might be a dime)
The issue was where Orko got He-Man's powers or something, I was too young back then to understand anything, I just looked at the pictures.
Captain America. I am still trying to figure out what issue it was. It was from my dad's stack of books from the late 60's and early 70s. It was about 18 years ago when I first read it. I didn't really read comics again until a couple years ago but Cap was the first character I got back into.
Now that I think about it, the first actual comic I've ever read was probably an old Barb Wire issue my Mom bought at random. After that came Spider-Man's Tangled Web (which was really confusing to me as a kid), and a Bionicle promotional comic. Maybe some Archie and Calvin and Hobbes, if those count.
The first comic I read was one of the early teen issues of Sonic the Hedgehog. But since that was a comic based on a video game, you might argue that he's not a "comic character" proper. Likewise when I started reading Knuckles.
After that, you have to jump about a decade forward, when I started reading Ultimate Spider-Man.
Years ago my dad bought be a stack of random, old-ish comics. I've just looked through them and a couple were from the Azrael/Knightfall stuff. I'm not quite sure which one I read first, at the time I wasn't a big comic book reader. The first comic series I started to read monthly was the New 52 Green Lantern. So the first comic I can remember reading first was issue 1 of Green Lantern. Pretty boring compared to some others :P
Batman Long Halloween. Though the first one I actually bought was Batman Year One. (As you can probably tell I took a pretty conventional approach. Starting with the classics.)
I've branched out pretty far since then. I can't imagine how deprived I'd be if I hadn't explored comics. Pretty much my favorite hobby, yet more often my unhealthy obsession.
Probably Donald Duck, Mickey Mouse or another disney character (where I live there a collected in a weekly comic). Then there was the Archie TMNT and probably a few issues of Phantom as the first superhero books. The first superhero from the big two was Spider-man later followed by spawn (yeah he is not from the big two). Besides Donald Duck none of this was bought regularly. Spider-man became the first superhero I bought regularly around 2002.
Silver age Batman. I can't remember much, but there was one issue where Batman & Robin are looking at teeth set marks or something? and I also remember the issue where Thomas Wayne was Batman.
I didn't read them for very long, because all other comics that I read were with self-contained stories that only lasted one issue, and so I couldn't wrap my head around the longer running stories and different writers and artists (it wasn't made any easier by only buying the occasional issue).
Not sure if I could read at that time, but my brother bought an Action Comics (fortress of solitude cover) and a World's Finest (faceless superman and green arrow). Brother did not buy comics again. Later on I bought for myself Superboy & Legion (Anti-Lad).