A novel electrochemical oxidative sulfonylation-azidation of alkenes is accomplished by using sulfonyl hydrazide and trimethylsilyl azide (TMSN3) for the one-pot and green synthesis of β-azidoarylsulfone, which involves the direct construction of new C-S and C-N bonds. Notably, neither exogenous oxidants/additives nor metal catalysts are required for this method. In addition, this electrochemical strategy features mild conditions and wide substrate scope and has been proved to be a radical pathway by mechanistic studies.