Metastructured photoanode design based on p-n heterostructure film for enhanced photoelectrochemical and photoelectrocatalytic activities is reported, which mainly consists of four layers of Au film, n-ZnO film, p-Cu2O film or pCo3O4 and Au NPs. p-type Cu2O or Co3O4 film and n-type ZnO film are produced by using electrodeposition or hydrothermal method and sputtering depositionm, and subsequent annealing process. The Cu2O film formed by electrodeposition was obtained high carrier concentration, which resulted in large internal electric field between Cu2O and TiO2 interface. Thus, photo-generated charge carriers were efficiently led to charge separation. The Au NPs/Cu2O/ZnO/Au film shows a remarkable enhancement in the photocurrent density in the UV-visible region, compared with bare ZnO film. Metal-hetero junction structure effectively absorbed visible light by the surface plasmon resonance and efficiently separated electron-hole pairs in the photoelectrode.