Antimony sulfide thin films (300 nm) have been deposited on glass substrates at 1–10°C from chemical bath. When heated these become crystalline and photoconductive with optical band gap (direct) of 1.7 eV. Thin films formed from chemical baths containing SbCl3 and sodium selenosulfate are of mixed phase Sb2O3/Sb2Se3, which when heated in the presence of Se-vapor converts to single phase Sb2Se3 film with optical band gap of 1.1 eV. Such films possess dark conductivity of 10-8 ohm-1cm-1 and show photosensitivity of two orders. Reaction of Sb2S3-CuS in nitrogen at 400°C produces crystalline, photoconductive p-type CuSbS2 with optical band gap (direct) of 1.5 eV. By controlling the deposition and heating condition, (i)Sb2S3-(p)CuSbS2 layer is formed, which is utilized in a photovoltaic structure, (n)CdS:In-(i)Sb2S3-(p)CuSbS2, with a Voc of 345 mV and Jsc 0.18 mA/cm2 under 1 kW m-2 tungsten halogen illumination. In the case of a structure, CdS:Cl-Sb2S3-Cu2-xSe, Voc of 350 mV and Jsc of 0.5 mA/cm2 are observed.