Thin films of tin selenide (SnxSey) with an atomic ratio of , 1 and 1.5 were prepared on a glass substrate at T = 470°C using a spray pyrolysis technique. The initial materials for the preparation of the thin films were an alcoholic solution consisting of tin chloride (SnCl4centerdot 5H2O) and selenide acide (H2SeO3). The prepared thin films were characterized by X-ray diffraction (XRD), scanning electron microscopy, scanning tunneling microscopy, scanning helium ion microscopy, and UV-vis spectroscopy. The photoconductivity and thermoelectric effects of the SnxSey thin films were then studied. The SnxSey thin films had a polycrystalline structure with an almost uniform surface and cluster type growth. The increasing atomic ratio of r in the films, the optical gap, photosensitivity and Seebeck coefficient were changed from 1.6 to 1.37 eV, 0.01 to 0.31 and −26.2 to −42.7 mV/K (at T = 350 K), respectively. In addition, the XRD patterns indicated intensity peaks in r = 1 that corresponded to the increase in the SnSe and SnSe2 phases.