Nature Catalysis, Published online: 28 April 2026; doi:10.1038/s41929-026-01528-5 Stereocontrol over radical intermediates is highly sought after in asymmetric organic synthesis, yet current approaches remain limited and difficult to generalize. A photobiocatalytic strategy employing thiamine diphosphate (ThDP)‑dependent enzymes now achieves simultaneous and precise control over two prochiral radical intermediates, enabling new‑to‑nature C(sp3)–C(sp3) bond formation with high enantio‑ and diaste