Here, we propose a novel hydrothermal method for the synthesis of high-quality, compact, and phase-pure Sb2Se3 films in substrate configuration. By introducing Sn 2+ cations into the precursor solution, surface defects of Sb2Se3 films are significantly suppressed, reducing from 2.67×10 12 cm -2 (undoped Sb2Se3) to 8.64×10 11 cm -2 (Sn-doped Sb2Se3). Meanwhile, the carrier density is increased in the Sn-doped Sb2Se3 film. These advantages of Sn doping result in greatly enhanced PEC performance with a notable improvement in the fill factor (FF).