Three different synthetic routes, including solid-state reaction, sol–gel and hydrothermal methods are successfully used for preparation of Li3V2(PO4)3/C. Ascorbic acid is used as a reducing agent and/or as a chelating agent. The Li3V2(PO4)3/C synthesized by hydrothermal method with fine particles exhibits lower impedance and smaller potential difference values between oxidation and reduction peaks than those by solid-state reaction and sol–gel methods. Thus as cathode material for Li-ion batteries, the Li3V2(PO4)3/C synthesized by hydrothermal method shows higher discharge capacity, better rate capability and cyclic performance. Even at a high charge–discharge rate of 10C, it still can deliver a discharge capacity of 101.4mAhg−1 and 106.6mAhg−1 in the potential range of 3.0–4.3V and 3.0–4.8V, respectively. The hydrothermal synthesis has been considered to be a competitive process to prepare Li3V2(PO4)3/C cathode materials with excellent electrochemical performances.