Antimony sulfide (Sb 2 S 3 ) has been recognized as a catalytic material for splitting water by solar energy because of its suitable narrow band gap, high absorption coefficient, and abundance of elements. However, many deep-level defects in Sb 2 S 3 result in a significant recombination of photoexcited electron−hole pairs, weakening its photoelectrochemical performance. Here, by using a simple hydrothermal and spin-coating method, we fabricated a step-scheme heterojunction of Sb 2 S 3 /α-Fe 2 O 3 to improve the photoelectrochemical performance of pure Sb 2 S 3 . Our Sb 2 S 3 /α-Fe 2 O 3 photoanode has a photocurrent density of 1.18 mA/cm 2 at 1.23 V vs reversible hydrogen electrode, 1.39 times higher than that of Sb 2 S 3 (0.84 mA/cm 2 ). In addition, our heterojunction has a lower onset potential, a higher absorbance intensity, a higher incident photon-to-current conversion efficiency, a higher applied bias photon-to-current efficiency, and a lower charge transfer resistance compared to pure Sb 2 S 3 . Based on ultraviolet photoelectron spectroscopy, we constructed a step-scheme band structure of Sb 2 S 3 /α-Fe 2 O 3 to explain its photoelectrochemical enhancement. This work offers a promising strategy to optimize the performance of Sb 2 S 3 photoelectrodes for solar-driven photoelectrochemical water splitting.