An organo-photocatalytic sulfonylimination of alkenes was developed by employing readily available N -sulfonyl ketimines as bifunctional reagents. This transformation, featuring prominent functional group tolerance, provides a direct and atom-economic approach for the synthesis of valuable β-amino sulfone derivatives as a single regioisomer. In addition to terminal alkenes, internal alkenes participate in this reaction with high diastereoselectivity. N -Sulfonyl ketimines with aryl or alkyl substituents were found to be compatible with this reaction condition. This method could be applied in the late-stage modifications of drugs. Additionally, a formal insertion of alkene into cyclic sulfonyl imine was observed, affording a ring expansion product.