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Green plants convert sunlight into high-energy chemicals by coupling solar-driven water oxidation in the Z-scheme and CO2 fixation in the Calvin cycle. Here, we have interfaced formate dehydrogenase from Clostridium ljungdahlii (ClFDH) with a TiO2-deposited CuFeO2 and CuO-mixed (ClFDH-TiO2|CFO) electrode. In the biohybrid photocathode, TiO2 layer enhances the photoelectrochemical (PEC) stability of the labile CFO photocathode and facilitates the transfer of photoexcited electrons from the CFO to ClFDH. Furthermore, inspired by the natur