We report a Cu(I)-photocatalyzed three-component coupling process to achieve regioselective, vicinal 1,2-aminosulfonylations of alkenes. The critical aspect of this methodology is found in the utilization of in situ generated photoactive Cu(I)-amine substrate complexes, which facilitate the formal oxidation of Cu(I) to Cu(III) in a stepwise manner. In this way, the conceivable two-component chlorosulfonylation of alkenes is effectively suppressed, allowing the combination of styrene derivatives, sulfonyl chlorides, and amines. Furthermore, this protocol can be used to facilitate late-stage functionalization, thereby enabling the diversification of biomolecules.