In summary, we have developed a visible-light driven enantioselective radical addition to imines by the combined use of chiral phosphoric acid and benzothiazoline derivatives. A range of aromatic aldimines participated in the radical addition, and high to excellent enantioselectivities were observed. Several alkyl and acyl radicals were suitable for this reaction system. The use of aromatic aldimines bearing the 3,4,5-trimethoxyphenyl group on nitrogen is critical and the N-aryl moiety can be removed quantitatively without loss of enantioselectivity to give chiral primary amines. Mechanistic studies revealed that the key step of the reaction is the excitation of the chiral phosphoric acid-imine complex, which has high reduction potential (Ered* = +1.58 V) for oxidizing benzothiazolines. Furthermore, the asymmetric carbon center of benzothiazoline is racemized under the reaction conditions and this skeleton is crucial for the interaction with chiral phosphoric acid to exhibit high enantioselectivity.