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Photoelectrochemical (PEC) water splitting on illuminated semiconductors plays an increasing role in alternative energy devices because of the need for clean and sustainable energy. However, the overall efficiency of the process is still very low and requires further improvement for widespread application. Herein, we report that the PEC performance of WO3 can be optimized by constructing a WO3@α-Fe2O3 heterojunction nanosheet array to expand the spectral range of light absorption and promote photogenerated electron-hole separation/transfer. This heterojunction photoanode exhibit a pronounced photocurrent response of 1.66 mA cm−2, a high incident photon-to-current conversion efficiency of ∼73.7 % at 390 nm, and an excellent photostability of 100 %, all at 1.23 V versus reversible hydrogen electrode. Therefore, our approach has great potential for designing efficient hybrid photoanodes for PEC water-splitting systems. [ABSTRACT FROM AUTHOR]