The Question comes right to mind. Steve Ditko, who created The Question along with similar character Mr. A (the original) and inspired Rorschach, was a genius. The Question was great in every appearance, but I particularly like how he sided with Huntress against Green Arrow and Black Canary, that episode and those two parings in opposition being among my favorites.
Supergirl comes to mind next. What's scarier than a teenager? A Kryptonian teenager under a yellow sun! Yet she's just so much Superman's cousin, so good natured, that she's still a hero. I especially love her in the JLU premiere, where she sticks out her tongue at Jon Stewart's hard-necked fomer marine GL, only to smile with a bit of embarrassment at the sympathetic Green Arrow, who also doesn't care for the former marine. That episode too features some great interplay among characters, as Ollie doesn't think much of Captain Atom either, neither his military manner nor his connection to atomic energy. "I think you're what I protested in college."
Captain Atom is another great character (and also co-created by Ditko). I love the polite, military way he disses Green Arrow in that episode, and the way he uses the same tone when ordered by the US government to stop Superman from rescuing The Question. I love the way that Superman pounds him down, but then takes him with, because "he's Justice League." (In fairness, that's something I loved about Superman, but still, it's a great interaction.) I love the way Captain Atom manages to come to the rescue on the Watchtower when Galatea shows up controlling an army of mindless Ultimen.
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