By Electrostatic spinning method，it was prepared NiO - ZnO oxide nanofibers with different mass ratios. Their structure, composition and morphology were characterized by XRD, XPS, BET, SEM and TEM respectively and their electrochemical properties were also investigated by electrochemical workstation. The results showed that when the nickel and zinc ratio was 10:1, the obtained nanofibers possessed large surface area of 71.425m2/g and were porous with mesoporous diameter of 13.37nm. Electrochemical tests showed that the 10:1 sample had clearer redox peak and more large discharge capacity than the pure NiO fibers, in which the value of the capacity had risen from 331F/g to 441F/g under the current density of 1A/g. Eespecially, it still remained 81.2% of starting value after 1000 cycles, and its maximum capacitance was 461F/g at 0.5A/g, which showed the excellent electrochemical performance of the sample.The process of the nanofiber synthesis was also introduced.