Despite remarkable advances in photoenzymatic methodologies, the development of photoenzymatic multicomponent reactions remains a significant challenge. In this Highlight, we showcase a recent breakthrough by Prof. Xiaoqiang Huang and co-workers, who achieved enantioselective triple-component radical sorting via visible light-induced biocatalysis under mild conditions. This innovative approach opens new avenues for the synthesis of complex molecules with high precision and efficiency, marking a remarkable advance in the field of enzymatic photocatalysis.