The Li3V2(PO4)3/C composite (LVP) including nanorods and irregular solids were successfully prepared by a sol–gel method. The influences of different precursors on the LVP cathode materials were investigated by using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), particle size distribution measurement and electrochemical methods. The LVP/C electrodes present good rate capability and excellent cyclic performance when they cycle in the range of 3.0–4.3V. The LVP1/C composite prepared by NH4H2PO4, LiOH, NH4VO4 and citric acid delivers the initial discharge capacity of 109.6mAhg−1 at 20C discharge rate and it still maintains 56.9mAhg−1 after 450 cycles, with the discharge capacity retention of 51.9%. For the LVP2/C composite synthesized by LiH2PO4, NH4VO4 and citric acid, however, the discharge capacities in the 1st and 450th cycles at 20C discharge rate are 107.1 and 96.2mAhg−1, respectively, with only 10.2% loss. The excellent rate capacity is attributed to the pure phases, nanorod structure, small particles and uniform carbon coating.