A new electrochemical intermolecular 1,2‐aminosulfonylation of alkenes with sulfinates and amines is achieved by utilizing balanced three‐component interactions and reactivity differentiation. This strategy can be applicable to a wide range of amines, including primary and secondary amines, thus enabling alkene aminosulfonylation for producing diverse functionalized 2‐sulfonylethan‐1‐amines without the need of additive redox catalysts, metal catalysts and chemical oxidants. [ABSTRACT FROM AUTHOR]