A novel Li3V2(PO4)3/C nanofibers composite has been first prepared by a facile and environmentally friendly electrospinning method using NH4VO3, CH3COOLi, poly (4-vinyl) pyridine (PVP) and citric acid aqueous solution as raw materials. The composite is investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM) and electrochemical tests. The Li3V2(PO4)3/C nanofibers composite exhibits excellent cycle performance and good rate capability in the voltage range of 3.0–4.8 V. The composite displays a high discharge capacity of 190 mAh g−1 (close to theoretical capacity of 197 mAh g−1) at 0.1 C (19.7 mA g−1). Even at a high-rate of 20 C, the composite presents the discharge capacity of 132 mAh g−1 and good cycle performance. The outstanding electrochemical performance is attributed to the particular morphology and microstructure of Li3V2(PO4)3/C nanofibers composite that dispersive Li3V2(PO4)3 nanofibers and carbon nanofibers aggregate to form nanofibers composite with mesopores and large surface area.