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When Justice League Unlimited was being formed, Green Arrow was immediately asked to join--but, despite repeated requests, the League never heard back from Green Arrow. Although he was concerned that if he joined the League, they would be too focused on the giant monsters and global threats, and that no one would look out for the "little guy," Green Arrow eventually aided Green Lantern, Captain Atom, and Supergirl in a fight against a rogue nuclear monster, Brimstone, in Chong-Mi. With his excellent skill with a bow, he makes a great and very much needed addition to the team.
Green Arrow and Black Canary began getting "serious" after attempting to free Wildcat from a prize-fighting ring. Green Arrow was also the loudest voice in protest of the Justice League's disbanding, something he helped reverse during the Justice League's speech.