A convenient and practical multicomponent strategy for the sulfenoamination of alkenes was realized, which using free‐thiols as the sulfur‐reagent, NIS both as radical initiator and an N‐nucleophile. This protocol excellent in terms of transition‐metal‐free, good functional group tolerance, easily available substrates and facile scale‐up. And provided a direct‐ and general way to synthesize various β‐succinimide sulfides with high regioselectivity.