An I2-mediated approach for selective C-H functionalization of unprotected aniline derivatives for synthesizing benzils and quinoxaline derivatives from sulfoxonium ylides has been described. Aniline derivatives and sulfoxonium ylides ornamented with different functional groups showed good compatibility. They afforded the corresponding products with moderate to high yields via a mild and simple procedure. Finally, we validated the practicality of this method by scaling up the reaction and further conversion of the synthesized derivatives into other valuable molecules.