A spontaneously formed ZnO/ZnWOx bilayer resistive memory via an interfacial engineering by one-step sputtering process with controllable high resistance states was demonstrated. The detailed formation mechanism and microstructure of the ZnWOx layer was explored by X-ray photoemission spectroscopy (XPS) and transmission electron microscope in detail. The reduced trapping depths from 0.46 to 0.29 eV were found after formation of ZnWOx layer, resulting in an asymmetric I-V behavior. In particular, the reduction of compliance current significantly reduces the switching current to reach the stable operation of device, enabling less energy consumption. Furthermore, we demonstrated an excellent performance of the complementary resistive switching (CRS) based on the ZnO/ZnWOx bilayer structure with DC endurance >200 cycles for a possible application in three-dimensional multilayer stacking.