A metal-free approach for synthesizing hybrid quinoxaline derivatives from sulfoxonium ylide and a 1,5-bisnucleophilic N-heterocycle mediated by elemental sulfur is presented to illuminate the [5+1] cascade cyclization sequence. Largescale synthesis and postsynthetic functionalizations for the annulative π-extension and intramolecular aza-annulation reactions reveal the potential utility and actualize the fabricated approach.