The common photoanode for PEC, BiVO4, exhibits inefficient charge transport. A novel composite photoanode, BiVO4/TiO2 (001)/Ti3C2 MXene, was fabricated by thin-coating TiO2 (001) and Ti3C2 MXene flakes onto BiVO4 films. The addition of Ti3C2 MXene thin flakes onto BiVO4/TiO2 and BiVO4/TiO2 (001) films significantly increases the photocurrent density 67% and 82% to approximately 1.5 and 2 mA.cm-2, respectively (at 1.23 VRHE under 1.5G AM illumination). Besides, the photocurrent density of the TiO2 (001)-based photoanode surpasses that of the TiO2-based photoanode. This is attributed to the high density of unsaturated coordination sites on (001) facets, which act as efficient electron acceptors and provide abundant active sites for water oxidation. The combination of TiO2 (001) and Ti3C2 MXene enhances PEC water oxidation reaction performance by serving as a co-catalyst, improving charge-transfer of photogenerated carriers and reducing charge recombination of BiVO4. This ternary heterostructure represents a promising strategy for effective PEC water oxidation. © 2026