Aryl sulfinamides are valuable intermediates and functional motifs in organic synthesis, with broad utility in pharmaceutical and agrochemical development. However, their broader application has been limited by underdeveloped synthetic methods, often requiring conventionally prefunctionalized aryl/alkenyl halides or organometallic reagents, protected sulfinylamine reagents, and harsh reaction conditions. Herein, we report a photo/copper-catalyzed sulfinamidation of arenes and alkenes, employing aryl and alkenyl sulfonium salts as radical linchpins. This protocol proceeds under mild conditions, exhibits broad functional group tolerance, and enables highly regioselective late-stage functionalization of complex molecules. The method provides streamlined access to diverse aryl S(IV) and S(VI) derivatives, offering a powerful platform for drug discovery and the modular synthesis of bioactive compounds.