NiO@Co3O4 core-shell oxide nanofiber (NF) with diameter of 200 nm were prepared by a simple sol-gel based on electrospinning method. When applied as an anode material for lithium-ion batteries (LIBs), it delivers stable cyclic performance with specific capacity of 487 mAh g(-1) after 200 cycles at 0.5 C. Moreover, high rate capabilities are observed in each current density in the core-shell nanofiber. This indicates that the electrochemical performance of the core-shell nanostructure significantly enhances reversible capacity and high rate capabilities over NiO and Co3O4 nanofibers. Such an enhanced electrochemical performance is attribute to the synergistic effect between each component.