Resistive switching devices are recognized as candidates for next-generation memory devices in that they can replace conventional memory devices. In these devices, a WOX film deposited by RF magnetron sputtering with a significant number of oxygen vacancies exhibits a resistive switching property and does not involve the use of a forming process. The resistive switching mechanism involves the hopping of electrons through the sub-band states of the oxygen vacancies in E-field-driven electromigration. X-ray photoemission spectroscopy, ultra-violet photoemission spectroscopy, and transmission electron microscopy-electron energy loss spectroscopy were performed to analyze local variations in the O-vacancies and in the electronic band structure of a WOX thin film. The band structure is responsible for the correlation between the motion of the electrons under the interface effect at the electrodes with the change in the resistance and the bias-polarity dependence of the I-V property of the device. The optimized metal-insulator-metal structure (Pt/WOX/Au), which has an asymmetric electrode and many oxygen vacancies, gives rise to excellent resistive-switching properties with a high on/off ratio on the order of 105 times, a low set voltage of <0.34 V, and a uniform DC cyclic performance in the order of 1500 cycles at room temperature. These specifications can be further adopted for application to non-volatile memory-device applications.