A VOx/C nanofiber composite has been synthesized by using the electrospinning method and studied as an anode material for lithium ion batteries. The VOx/C nanofibers mainly are composed of VO2, V2O5, and carbon. The VOx/C nanofibers exhibited excellent electrochemical performance. A high discharge capacity of 850 mA h g−1 can be retained after 100 cycles at the current density of 40 mA g−1. A discharge capacity of 550 mA h g−1 still can be delivered after 100 cycles, when the current density is increased to 1000 mA g−1.