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.