This article describes the use of enantioenriched arylsulfinylamides as multifunctional reagents for the efficient asymmetric, intermolecular aminoarylation of alkenes. Under mild photoredox conditions, the nitrogen atom of the arylsulfinylamide adds to the double bond, followed by a 1,4-translocation of the aromatic ring, producing enantiomerically enriched aminoarylation products. The sulfinyl group acts as a traceless chiral auxiliary, eliminating in situ under mild reaction conditions. This method allows the access to optically pure β,β-diarylethylamines, aryl-α,β-ethylenediamines, and α-aryl-β-aminoalcohols, which are important motifs in pharmaceuticals, bioactive natural products, and ligands for transition metals. The reaction tolerates a wide range of N-atom donors and is compatible with various functional groups, demonstrating excellent regio-, diastereo-, and enantioselectivity. Mechanistic studies reveal that the reaction mechanism involves multiple pathways, depending on the type of olefinic partner, with the C–N bond formation being stereocontrolled by the chirality of the sulfoxide.This article describes the use of enantioenriched arylsulfinylamides as multifunctional reagents for the efficient asymmetric, intermolecular aminoarylation of alkenes. Under mild photoredox conditions, the nitrogen atom of the arylsulfinylamide adds to the double bond, followed by a 1,4-translocation of the aromatic ring, producing enantiomerically enriched aminoarylation products. The sulfinyl group acts as a traceless chiral auxiliary, eliminating in situ under mild reaction conditions. This method allows the access to optically pure β,β-diarylethylamines, aryl-α,β-ethylenediamines, and α-aryl-β-aminoalcohols, which are important motifs in pharmaceuticals, bioactive natural products, and ligands for transition metals. The reaction tolerates a wide range of N-atom donors and is compatible with various functional groups, demonstrating excellent regio-, diastereo-, and enantioselectivity. Mechanistic studies reveal that the reaction mechanism involves multiple pathways, depending on the type of olefinic partner, with the C–N bond formation being stereocontrolled by the chirality of the sulfoxide.