NiO@Co3O4 nanofibers with different mass ratio and different additives were prepared by electrospinning process. The characterizations of the nanofibers are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Electro-chemical properties are characterized by cyclic voltammetry, galvanostatic charge/discharge measurements, and electrochemical impedance spectroscopy. Results show that the NC-1 nanofibers are hollow tube and comprised of many NiO and Co3O4 sheets. Furthermore, the NC-1 nanofibers have the highest specific capacitances (788 F.g(-1) at the current density of 5 mA.cm(-2)) and excellent cyclic performance (decreases 7% of the initial capacitance after 1000 cycles).