An efficient I₂-catalyzed cascade coupling protocol was developed for the synthesis of pyrrolo[1,2-a]quinoxaline and imidazo[1,5-a]quinoxaline derivatives via sp³ and sp² C–H cross-dehydrogenative coupling. A nontoxic, readily available catalyst, I₂, and an oxidant, DMSO, were used in this metal-free process. The target compounds were obtained in good-to-excellent yields with a broad substrate scope.