The paper reports the development of a novel photobiocatalytic method for the asymmetric oxidative cross-coupling of amino acids and organoboron reagents, enabling the stereoselective synthesis of non-canonical amino acids (ncAAs). This process involves the cooperative use of visible-light photoredox catalysts, engineered pyridoxal-5′-phosphate (PLP)-dependent enzymes, and a stoichiometric oxidant. The key steps include the formation of a transient carbon-centered radical by the photoredox catalyst, which then adds to the α-carbon of an external aldehyde intermediate formed by the PLP-dependent enzyme. This radical addition is followed by a single-electron oxidation by the photoredox catalyst, leading to the formation of the final product. The method allows for the synthesis of ncAAs with contiguous stereocenters and α-tetrasubstituted stereocenters, which are challenging to access using conventional methods. The study also includes enzyme engineering to improve the efficiency and stereoselectivity of the reaction, demonstrating the potential for scalable synthesis. Computational studies support the proposed reaction mechanism, highlighting the importance of the irreversible benzyl radical addition in the enantio- and regioselectivity of the catalytic cycle.The paper reports the development of a novel photobiocatalytic method for the asymmetric oxidative cross-coupling of amino acids and organoboron reagents, enabling the stereoselective synthesis of non-canonical amino acids (ncAAs). This process involves the cooperative use of visible-light photoredox catalysts, engineered pyridoxal-5′-phosphate (PLP)-dependent enzymes, and a stoichiometric oxidant. The key steps include the formation of a transient carbon-centered radical by the photoredox catalyst, which then adds to the α-carbon of an external aldehyde intermediate formed by the PLP-dependent enzyme. This radical addition is followed by a single-electron oxidation by the photoredox catalyst, leading to the formation of the final product. The method allows for the synthesis of ncAAs with contiguous stereocenters and α-tetrasubstituted stereocenters, which are challenging to access using conventional methods. The study also includes enzyme engineering to improve the efficiency and stereoselectivity of the reaction, demonstrating the potential for scalable synthesis. Computational studies support the proposed reaction mechanism, highlighting the importance of the irreversible benzyl radical addition in the enantio- and regioselectivity of the catalytic cycle.