Arylethylamines are privileged motifs in bioactive compounds and pharmaceuticals. Described here is a novel photocatalytic aminoarylation of styrenes to afford arylethylamines utilizing commercially available reagents. Aryl iodides undergo single-electron reduction to yield an aryl radical intermediate, enabling subsequent addition to styrenes. The resulting benzylic radical then undergoes oxidation to a carbocation and is trapped by a nucleophilic amine. Mechanistic studies, including Stern-Volmer fluorescence quenching studies and radical trapping experiments, support the proposed catalytic cycle.