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Semiconducting cuprous oxide films were electrodeposited onto conducting glasses coated with Indium Tin Oxide (ITO) using potentiostatic method. The electrodes were examined by means of X-Ray Diffraction (XRD) and X-ray Photoelectron Spectrum (XPS). The results indicate that the prepared films are cubic Cu2O crystals, and annealing enhances the size and preferred orientation of the films. The photoelectric conversion mechanism of semiconducting ITO/Cu2O electrodes in 0.1 mol/L potassium sulfate (K2SO4) solution is further discussed by using Linear Sweep Voltammetry (LSV) method. The differences of photoelectric conversion of electrodes are reasonably deduced and proved through surfactant modifying, annealing or not, respectively.