The study sets out to show the positive impact of sulfur vacancy engineering on the structural, morphological, optical, electrical, and photoelectrochemical (PEC) properties of Sb₂S₃ films synthesized using the spin coating technique. The produced films were exposed to γ-irradiation with different doses from 0 to 20 kGy. We have demonstrated the formation of sulfur vacancies and loss of oxygen content in the irradiated samples. XRD measurements revealed that all films exhibit a polycrystalline structure, and the crystallite size increases with the rising radiation dose, reaching the highest value of 87.4 nm measured for the Sb₂S₃ film irradiated with 15 kGy. The surface roughness of the irradiated samples increases with increasing γ-irradiation dose. The increase in surface roughness not only raises the active sites but enhances the conductivity of the Sb₂S₃ material as well. The wettability properties of the irradiated films were affected by γ-irradiation doses and the sample irradiated with 15 kGy exhibited the lowest hydrophobicity compared to others. The Hall measurements reveal that irradiated samples exhibit p-type semiconductor behavior. The optical band gap decreased progressively from 1.78 eV to 1.60 eV up to the irradiation dose of 15 kGy and slightly increased thereafter. The irradiated sample with 15 kGy showed a maximum photocurrent density of ca. 1.62 mA cm⁻² at 0 V vs. reverse hydrogen electrode (RHE) under AM 1.5 G illumination with applied bias photon-to-current efficiency (ABPE) of 0.82% at 0.47 V vs. RHE, suggesting superior PEC water splitting performance compared to other samples. At 0 V vs. RHE and 648 nm, the incident photon current efficiency (IPCE) and absorbed photon current efficiency (APCE) of the photocathode irradiated with 15 kGy are significantly higher than those of the other photocathodes with values of 9.35% and 14.47%, respectively. Finally, Mott–Schottky measurement was also performed on all photocathodes to estimate their acceptor density and flat band potential.