Programmable Molecular Hubs Orchestrate Orthogonal CO 2 ‐to‐CH 4 Photocatalysis and Biomass Valorization

Semi‐artificial photosynthesis that merges biocatalytic specificity with engineered materials enables sustainable solar fuel production, yet it remains constrained by low solar‐to‐chemical efficiency and limited scalability. Here, we present a supramolecular strategy by programmatically integrating photocatalysts, biocatalysts, and cofactors on a single protein scaffold, and realize the coupling of photocatalytic CO 2 ‐to‐CH 4 conversion with enzymatic biomass upgrading. A rationally designed molecular hub—comprising switchable μ ‐oxo‐bridged bis(Fe III ‐porphyrin) units and NADH mimics—drives deep CO 2 reduction to CH 4 at rates up to 32 000 µmol g −1 h −1 with >99% selectivity and a total apparent quantum efficiency of 1.82%. Modular tethering of diverse dehydrogenases activates inert C(sp 3 )─H bonds, delivering C 2─ C 6 chemicals, including enantioenriched compounds ( ee >96%). This programmable platform establishes a redox‐balanced strategy for solar‐driven synthesis of fuels and fine chemicals from CO 2 and low‐value feedstocks, unifying abiotic and biotic catalysis within a single framework.