A method for the synthesis of α-hydroxyl and α-amino pyridinyl esters via photoreductive dual radical cross-coupling catalyzed by the super-organoreductant CBZ6 has been developed. A wide range of 2-pyridinylation and 4-pyridinylation of either α-ketoesters or imine derivatives has been achieved. The applications in the synthesis of pyridinyl amino-hydroxyl acids as well as a new chiral oxazoline ligand have also been accomplished.