Number one would have to be Will Eisner. Take a look at Minor Miracles… his use of wash is insane. He was like Michelangelo.
I would also put in Joe Schuster. Though his drawings were very simple, his rendition of Superman (not the costume itself, but the character wearing it) is definitive, and it laid the groundwork for the entire superhero genre–which obviously dominates the history of comics, for better or worse.
Frank Miller is in, specifically for his work on Sin City. Marv’s walk in the rain from the first Sin City is probably my all-time favorite Frank Miller piece.
Neal Adams is in. Just about anything he ever did with Batman is fair game for an art book. He has the draftsmanship of Alex Ross, combined with the storytelling ability of Jack Kirby.
Robert Crumb is another obvious pick. His art style is so distinctive and so simple, but what he does with it is pretty outrageous. There’s a great documentary about him that shows him creating these intricate drawings with just a pad of paper and a Sharpie.
Tim Sale is great. I don’t read a lot of superhero comics, but he’s been involved in some pretty great stuff in relatively recent times. The Long Halloween is probably the best Batman artwork I can think of since David Mazzuchelli’s work on Year One.
Stuart Immonen is in, based purely on his work in Superman: Secret Identity. It is damn hard to make pencil drawings work as finalized art, but he did far better than just make it work. It enhances the story in a very powerful way, and the number one job of the comics artist is to work in service of the story.
Dave Gibbons is in. His artwork strikes the perfect balance between very humane realism and comic booky cartooning. He deserves as much credit for Watchmen as Alan Moore does. It was very much a partnership.
And I suppose I’d better mention Frank Quitely, since All Star Superman is the most exciting thing that’s happened in superhero comics in a very long time. His art really brings the stories to life.