Abstract The conditions of the electrodeposition of a thin film of polycrystalline ZnSe phase on copper substrate from aqueous baths were studied. The electrochemical behavior of Zn2+ and H2SeO3 species was investigated using cyclic voltammetry. Thin films were deposited potentiostatically on copper substrate and the influence of deposition parameters such as deposition potential, H2SeO3 and ZnSO4 concentration, and temperature of bath on the crystallinity and on the chemical composition of the film is discussed. The ZnSe layers were characterized by X-ray diffraction, X-ray energy dispersive spectroscopy and scanning electron microscopy.