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CuFeO₂ is recognized as a potential photocathode for photo(electro)chemical water splitting. However, photocurrents with CuFeO₂-based systems are rather low so far. In order to optimize charge carrier separation and water reduction kinetics, defined CuFeO₂/Pt, CuFeO₂/Ag, and CuFeO₂/NiOx(OH)y heterostructures are made in this work through a photodeposition procedure based on a 2H CuFeO₂ hexagonal nanoplatelet shaped powder. However, water splitting performance tests in a closed batch photoreactor show that these heterostructured powders exhibit limited water reduction efficiencies. To test whether Fermi level pinning intrinsically limits the water reduction capacity of CuFeO₂, the Fermi level tunability in CuFeO₂ is evaluated by creating CuFeO₂/ITO and CuFeO₂/H₂O interfaces and analyzing the electronic and chemical properties of the interfaces through photoelectron spectroscopy. The results indicate that Fermi level pinning at the Fe³⁺/Fe²⁺ electron polaron formation level may intrinsically prohibit CuFeO₂ from acquiring enough photovoltage to reach the water reduction potential. This result is complemented with density functional theory calculations as well.