A nano-MoO3/C composite was synthesized using the electrospinning method. Thermal analysis was used to determine the carbon content in the composite. The MoO3/C composite was characterized by X-ray diffraction, and the particle size and shape of the MoO3/C composite were observed by scanning and transmission electron microscopy. The results showed that the MoO3/C composite takes on the morphology of nanofibers, with the diameters of the nanofibers ranging from 50 to 200nm. The nanofibers are composed of amorphous nano-MoO3 and carbon, with the carbon content in the composite about 42% and the MoO3 content about 58%. The electrochemical properties of the MoO3/C composite were also investigated. The MoO3/C composite nanofiber electrodes exhibited both high reversible capacity and good cycling performance when cycled at room temperature in a 3.0–0.01V potential (vs Li/Li+) window at current density of 40mAg−1. The MoO3/C composite retained a discharge capacity of 710mAhg−1 after 100 cycles. When the load current density was increased to 800mAg−1, the MoO3/C composite still retained a discharge capacity of 300mAhg−1 after 100 cycles. The reasons for the outstanding electrochemical properties of the MoO3/C composite are also discussed.