Spray-pyrolysed SnIV-doped α-Fe2O3 photo-anodes were used for photo-assisted splitting of HS− ions in alkaline aqueous solutions, producing polysulfide (Sn2 −) ions together with hydrogen at the cathode. Subsequent aerial oxidation of polysulfide could be used to produce elemental sulfur. At an applied electrode potential of 1.07 V (RHE) and an irradiance of 5.6 kW m− 2, stable photocurrents of ca. 11 A m− 2 (2 × 10− 3 A W− 1) were recorded over 75 h, polysulfide concentrations increasing linearly with time. Despite being predicted thermodynamically to form iron sulfide(s) in sulfide solutions, such photo-anodes appeared to be stable. In comparison with conventional water splitting under alkaline conditions, the coupled processes of hydrogen sulfide ion oxidation and water reduction had a lower energy requirement.