A liquid-based sol–gel method was developed to synthesize nanocarbon-coated Li3V2(PO4)3. The products were characterized by XRD, SEM and electrochemical measurements. The results of Rietveld refinement analysis indicate that single-phase Li3V2(PO4)3 with monoclinic structure can be obtained in our experimental process. The discharge capacity of carbon-coated Li3V2(PO4)3 was 152.6mAh/g at the 50th cycle under 1C rate, with 95.4% retention rate of initial capacity. A high discharge capacity of 184.1mAh/g can be obtained under 0.12C rate, and a capacity of 140.0mAh/g can still be held at 3C rate. The cyclic voltammetric measurements indicate that the electrode reaction reversibility is enhanced due to the carbon-coating. SEM images show that the reduced particle size and well-dispersed carbon-coating can be responsible for the good electrochemical performance obtained in our experiments.