A distinctive aminocatalysis via α-imino radical is reported on the basis of SET oxidation of a secondary enamine. The combination of chiral primary amine catalysis and visible-light photoredox catalysis enables the enantioselective decarboxylative coupling of propiolic acid and β-ketocarbonyls to afford alkynylation adducts with high enantioselectivity. Mechanism studies indicate the reaction proceeds via an α-imino radical addition.