Plate-like Li3V2(PO4)3/C composite is synthesized via a solution route followed by solid-state reaction. The Li3V2(PO4)3/C plates are 40–100nm in thicknesses and 2–10μm in lengths. TEM images show that a uniform carbon layer with a thickness of 5.3nm presents on the surfaces of Li3V2(PO4)3 plates. The apparent Li-ion diffusion coefficient of the plate-like Li3V2(PO4)3/C is calculated to be 2.7×10−8 cm2 s−1. At a charge–discharge rate of 3C, the plate-like Li3V2(PO4)3/C exhibits an initial discharge capacity of 125.2 and 133.1mAhg−1 in the voltage ranges of 3.0–4.3 and 3.0–4.8V, respectively. After 500 cycles, the electrodes still can deliver a discharge capacity of 111.8 and 97.8mAhg−1 correspondingly, showing a good cycling stability.