Abstract
ABSTRACT
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.