The deposition potential affects the structural, morphological, optical, and electrochemical impedance spectroscopy properties of cuprous oxide (Cu2O) thin films formed on copper (Cu) substrates adopting a three-electrode electrochemical deposition procedure. XRD data revealed that the deposited films have a cubic structure established with desired (111) growth orientation. Scanning electron microscopy (SEM) images reveal that Cu2O film has very well three-sided pyramid-shaped grains which are equally spread over the surface of the Cu substrates and change substantially when the plating potential is changed. The photo-current density of prepared Cu2O thin films was increased from -1.41×10-4 to -3.01×10-4 A/cm2 with increasing the deposition potential of -0.3 to -0.6V, respectively. Further, Cu2O thin films obtained at -0.6V have the minimum charge transfer resistance (Rct) than Cu2O thin films synthesized at -0.3 to -0.5V, suggesting that Cu2O thin films produced at -0.6V have the highest electron transfer efficiency.