The light-harvesting Sb2S3 surface on mesoporous-TiO2 in inorganic–organic heterojunction solar cells is sulfurized with thioacetamide (TA). The photovoltaic performances are compared before and after TA treatment, and the state of the Sb2S3 is investigated by X-ray diffraction, X-ray photoelectron spectroscopy, and deep-level transient spectroscopy (DLTS). Although there are no differences in crystallinity and composition, the TA-treated solar cells exhibit significantly enhanced performance compared to pristine Sb2S3-sensitized solar cells. From DLTS analysis, the performance enhancement is mainly attributed to the extinction of trap sites, which are present at a density of (2–5) × 1014 cm−3 in Sb2S3, by TA treatment. Through such a simple treatment, the cell records an overall power conversion efficiency (PCE) of 7.5% through a metal mask under simulated illumination (AM 1.5G, 100 mW cm–2) with a very high open circuit voltage of 711.0 mV. This PCE is, thus far, the highest reported for fully solid-state chalcogenide-sensitized solar cells.