A mild transition-metal-free protocol to prepare 2,3-dialkylated tartaric acid esters has been developed by taking advantage of a visible light photoredox-catalyzed reductive dimerization of α-ketoesters with a combination of an organic dye photocatalyst and a Hantzsch-type 1,4-dihydropyridine hydrogen donor. A broad range of functional groups including cyclopropane, alkene, alkyne, 4-methoxybenzyl ether, acetal, silyl ether, carbamate, cyclic ether, cyclic thioether, bromoalkane, and -alkoxyphthalimide are well-compatible. By employing the visible light photoredox-catalyzed reductive coupling and the subsequent optical resolution, both enantioenriched diastereomers of 2,3-dialkylated tartaric acid could be acquired conveniently.