The improvement of photoinduced charge separation is the key for light-harvesting systems in both photovoltaic and photoelectrochemical solar cells. In this study, the charge separation efficiency has been modulated through varying the magnitude of interfacial electric field in p鈥搉 Cu2O homojunction films prepared by simple electrodeposition method. The photoelectrochemical and surface photovoltage measurements were used to investigate the behaviors of photoinducded charge carriers in different p鈥搉 Cu2O homojunction films. The results confirmed that the p鈥搉 Cu2O homojunction film which exhibited the highest charge separation efficiency resulted in the highest activity in photocatalytic reduction of methyl viologen. These implied that it is possible to achieve high charge separation efficiency via constructing a large magnitude of interfacial electric field within a semiconductor using a simple electrodeposition method.