A novel sol–gel method based on V2O5·nH2O hydro-gel was developed to synthesize nanocrystalline Li3V2(PO4)3/carbon composite material. In this route, V2O5·nH2O hydro-gel, NH4H2PO4, Li2CO3 and high-surface-area carbon were used as starting materials to prepare precursor, and the Li3V2(PO4)3/carbon was obtained by sintering precursor at 750°C for 4h in flowing argon. The sol–gel synthesis ensures homogeneity of the precursors and improved reactivity. The sample was characterized by XRD, SEM and TEM. X-ray diffraction results show Li3V2(PO4)3 sample is monoclinic structure with the space group of P21/n. The TEM image indicates that the Li3V2(PO4)3 particles modified by conductive carbon are about 70nm in diameter. The Li3V2(PO4)3/carbon system showed that the discharge capacities in the first and 50th cycle are about 155.3 and 143.6mAh/g, respectively, in the range of 3.0–4.8V. The sol–gel method is fit for the preparation of Li3V2(PO4)3/carbon composite material which may offer some favorable properties for commercial application.