A copper-catalyzed three-component reaction of in situ formed arynes, terminal alkynes, and O-benzoylhydroxylamines has been developed. By adjusting reaction conditions, the nucleophiles in this transformation can be extended from terminal alkynes to benzoxazoles. These procedures provide a modular and facile approach to o-alkynyl anilines and o-benzoxazolyl anilines from easily available substrates in only one step.