Abstract: MoO₂/C nanofiber composite films were prepared by electrospinning with mass ratios of ammonium molybdate (AMT) to pure polyvinyl alcohol (PVA) of 1:9,2:8,3:7;4:6, repectively. The microstructure of the film and electrochemical property of the corresponding electrode were studied. The results show that with increasing AMT to PVA mass ratio, the fiber size of MoO₂/C nanofiber composite film decreased, the fiber distribution became uniform, and the filament forming effect was improved. Moreover, the specific capacitance of the corresponding electrode increased, and the cycle performance was enhanced. When the AMT to PVA mass ratio was 4∶6, the filament forming effect of the film was the best, and the corresponding electrode had good structural stability in the charge and discharge cyclic process. Meanwhile its cycle retention rate, charge specific capacity, discharge specific capacity and charge-discharge efficiency all increased after 5 000 charge-discharge cycles, and the cycle performance was excellent.