Electrochemistry contributes a strong tool for the manufacture of molecules,addressing intractable chal-lenges in synthetic chemistry by enabling innovative reaction pathways.Herein,a bifunctional reagent,aqueous hydrochloric acid,is used to establish an electrochemical selective dual-oxidation approach that gives access to α-chlorosulfoxides from sulfides.This strategy presents broad substrate scope,high diastereoselectivity,and regioselectivity.The late-stage modification of amino acids and pharmaceutical derivatives further highlights the utility.Furthermore,detailed mechanistic studies reveal that the key success for this selective chemical transformation is the dual-oxidation process at the anode.This elec-trochemical dual-oxidation strategy may have wide universality;we anticipate diverse applications of this protocol across the many fields of chemistry.