Silver antimony selenide (AgSbSe2) thin films were prepared by heating sequentially deposited antimony sulphide (Sb2S3), silver selenide (Ag2Se) and Ag thin films in close contact with a selenium thin film. Sb2S3 thin film was prepared from chemical bath containing SbCl3 and Na2S2O3, Ag2Se from the bath containing AgNO3 and Na2SeSO3 and Se thin films from an acidified solution of Na2SeSO3, at room temperature on cleaned glass substrates. Ag thin film was deposited by vacuum thermal evaporation. The annealing temperature was varied from 300-390°C in vacuum (∼10−3 Torr) for 1 h. X-ray diffraction analysis showed the films formed at 350 °C was polycrystalline AgSb(S,Se)2 or AgSbSe2 depending on selenium thin film thickness. Morphology of these films was analyzed using Atomic Force Microscopy and Scanning Electron Microscopy. The elemental analysis was done using Energy Dispersive X-ray technique. Optical characterization of the thin films was done by optical transmittance spectra. The electrical characterizations were done using Hall effect and photocurrent measurements. A photovoltaic structure: Glass/ITO/CdS/AgSbSe2/Ag was formed, in which CdS was deposited by chemical bath deposition. J-V characteristics of this PV structure showed Voc=370 mV and Jsc=0.5 mA/cm2 under illumination using a tungsten halogen lamp.