In this work, based on the electrospinning method, pure Co₃O₄, pure MnO₂, and Co₃O₄ composite nano-fiber materials doped with different ratios of Mn⁴⁺ were prepared. XRD, XPS, BET and SEM tests were used to characterize the composition, structure and morphology of the materials. An electrochemical workstation was used to test the electrochemical performance of the materials. The results showed that the material properties had greatly improved on doping Mn⁴⁺ in Co₃O₄ nano-fibers. The relationship between the amount of Mn⁴⁺ doped in the Co₃O₄ composite nano-fiber material and its electrochemical performance was also tested and is discussed in this report. The results show that when n_Co : n_Mn = 20 : 2, the Co₃O₄ composite nano-fiber material had a specific surface area of 68 m² g⁻¹. Under the current density of 1 A g⁻¹, the 20 : 2 sample had the maximum capacitance of 585 F g⁻¹, which was obviously larger than that of pure Co₃O₄ nano-fibers (416 F g⁻¹). After 2000 cycles of charging/discharging, the specific capacitance of the 20 : 2 sample was 85.9%, while that of the pure Co₃O₄ nano-fiber material was only 76.4%. The mechanism of performance improvement in the composite fibers was analyzed, which demonstrated concrete results.