An electrospinning method was used to synthesize the Co3O4/NiO nanofibers, which then was sulfurized by solvothermal method in order to improve their electrochemical properties. The SEM pictures showed that sulfurized Co3O4/NiO nanofibers were irregular short nano-rods consisting of nanocrystalline particles; the BET tests showed that sulfuration is beneficial to improve the specific surface area of the fibers; the XPS showed that the existence of the valence state: Co2+, Co3+, Ni2+, Ni3+ and S2- in sulfurized sample, which was confirmed by XRD as Co3S4 and Ni0.96S, respectively. Especially, electrochemical tests showed that the sulfurized Co3O4/NiO nanofibers electrode delivers high specific capacity of 156.84mAhg(-1) at 1Ag(-1) and 151.07mAhg(-1) at 10Ag(-1) and after 1000 cycles, its capacity retention reaches 87.3% at 5Ag(-1). The mechanism of improving the electrochemical performance after sulfidation was also discussed in detail.