The monoclinic-type Li3V2(PO4)3 cathode material was synthesized via calcining amorphous Li3V2(PO4)3 obtained by chemical reduction and lithiation of V2O5 using oxalic acid as reducer and lithium carbonate as lithium source in alcohol solution. The amorphous Li3V2(PO4)3 precursor was characterized by using TG–DSC and XPS. The results showed that the V5+ was reduced to V3+ by oxalic acid at ambient temperature and pressure. The prepared Li3V2(PO4)3 was characterized by XRD and SEM. The results indicated the Li3V2(PO4)3 powder had good crystallinity and mesoporous morphology with an average diameter of about 30nm. The pure Li3V2(PO4)3 exhibits a stable discharge capacity of 130.08mAhg−1 at 0.1C (14mAg−1).