The Cu2O/TiO2 inverse opal heterojunction arrays were developed by electrochemical deposition of Cu2O nanoparticles on TiO2 inverse opal arrays. The Cu2O nanoparticles completely filled the inner pores of TiO2 inverse opal film (prepared by liquid phase deposition with an average thickness of 400 nm) and covered the entire area; exhibiting high crystalline properties of anatase and cubic phase from TiO2 and Cu2O, respectively. From asymmetric current- voltage profile, it was noticeable that a heterojunction was well formed for charge transport from Cu2O to TiO2 film resulting from the enhanced charge separation yield. In addition, increased photocurrent of 0.19 mA/cm2 (versus 0.08 mA/cm2 under dark condition) was obtained at ?0.35 V from the heterojunction structure in the 0.5M Na2SO4 solution.