CuSbSe2 thin films have been prepared by electrodeposition followed by rapid thermal annealing. Cyclic voltammetry tests were firstly used to investigate the electrodeposition mechanism. The most suitable deposition potential for films preparation was determined to be about −0.40V vs. SCE combining with cyclic voltammetry, composition and morphology analysis. Polycrystalline films with the main phase of CuSbSe2 and secondary phase Sb2Se3 were obtained after rapid thermal annealing for both Cu-rich and Cu-poor thin films. Both films show an optical band gap value of about 1.09eV. Photoelectrochemical (PEC) characterizations indicate that Cu-poor thin film has the better photoelectrical properties than those of Cu-rich thin film.