We report on the fabrication and photoelectrochemical(PEC) properties of a Cu2O thin film/ZnO nanorod array oxide p-n heterojunction structure with ZnO nanorods embedded in Cu2O thin film as an efficient photoelectrode for solardriven water splitting. A vertically oriented n-type ZnO nanorod array was first prepared on an indium-tin-oxide-coated glass substrate via a seed-mediated hydrothermal synthesis method and then a p-type Cu2O thin film was directly electrodeposited onto the vertically oriented ZnO nanorods array to form an oxide semiconductor heterostructure. The crystalline phases and morphologies of the heterojunction materials were characterized using X-ray diffraction and scanning electron microscopy as well as Raman scattering. The PEC properties of the fabricated Cu2O/ZnO p-n heterojunction photoelectrode were evaluated by photocurrent conversion efficiency measurements under white light illumination. From the observed PEC current density versus voltage (J-V) behavior, the Cu2O/ZnO photoelectrode was found to exhibit a negligible dark current and high photocurrent density, e.g., 0.77 mA/cm2 at 0.5 V vs Hg/HgCl2 in a 1 mM Na2SO4 electrolyte, revealing an effective operation of the oxide heterostructure. In particular, a significant PEC performance was observed even at an applied bias of 0 V vs Hg/ HgCl2, which made the device self-powered. The observed PEC performance was attributed to some synergistic effect of the p-n bilayer heterostructure on the formation of a built-in potential, including the light absorption and separation processes of photoinduced charge carriers.