A highly efficient acetoxylation reaction of N-aryl-arylsulfonamides has been developed, presumably proceeding via the selective functionalization of N-aryl C-H bonds.1-6 A stoichiometric amount of PhI(OAc)2 was generally employed as the oxidation reagent, and various para-acetoxylated sulfonamide derivatives had been generated in excellent yields.This chemistry endowed an economic synthesis of valuable acetoxylated sulfonamides through direct C-O bond formation processes.