AbstractDetermining cost-effective semiconductors exhibiting desirable properties for commercial photoelectrochemical water splitting remains a challenge. Herein, we report a Sb₂Se₃ semiconductor that satisfies most requirements for an ideal high-performance photoelectrode, including a small band gap and favourable cost, optoelectronic properties, processability, and photocorrosion stability. Strong anisotropy, a major issue for Sb₂Se₃, is resolved by suppressing growth kinetics via close space sublimation to obtain high-quality compact thin films with favourable crystallographic orientation. The Sb₂Se₃ photocathode exhibits a high photocurrent density of almost 30 mA cm⁻² at 0 V against the reversible hydrogen electrode, the highest value so far. We demonstrate unassisted solar overall water splitting by combining the optimised Sb₂Se₃ photocathode with a BiVO₄ photoanode, achieving a solar-to-hydrogen efficiency of 1.5% with stability over 10 h under simulated 1 sun conditions employing a broad range of solar fluxes. Low-cost Sb₂Se₃ can thus be an attractive breakthrough material for commercial solar fuel production.