One of the most promising methods to store and utilize sunlight energy is to convert it into hydrogen via water splitting reaction. In this study, pure-phase Cu 11 V 6 O 26 thin film photoanodes were prepared on a FTO-coated glass substrate for the first time by a low-cost solution-based spray pyrolysis method. The optical bandgap, band positions, flatband potential, chemical composition, photocurrent onset potential, photocurrent generation, incident photon to current conversion efficiency, photoelectrochemical stability, and O 2 production Faradic efficiency of Cu 11 V 6 O 26 were systematically researched. UV−vis results showed that Cu 11 V 6 O 26 has an ideal bandgap of ∼1.85 eV, which corresponds to a theoretical photocurrent of up to 15 mA/cm 2 for solar water splitting. Photoelectrochemical measurements showed the onset of a photoanodic current driven under AM 1.5 illumination and reaching incident-photon-to-current efficiencies exceeding ∼4% in near-neutral (pH 6.8) aqueous solutions. Meanwhile, the Cu 11 V 6 O 26 photoelectrodes showed excellent photoelectrochemical stability and nearly quantitative Faradic efficiency, which suggest that Cu 11 V 6 O 26 could be a promising photoanode material. The results of this study will significantly increase our fundamental understanding of Cu 11 V 6 O 26 performance in solar water splitting reactions. Moreover, these data could be transferred to other ternary metal oxides for the same applications.