Stoichiometric and lithium-rich Li3+xV2(PO4)3 (x=0.02,0.04,0.05,0.06) for lithium batteries was prepared by a carbon-thermal reduction (CTR) process. The properties of the Li3+xV2(PO4)3 were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and electrochemical measurement. The results show that the samples have monoclinic structure, without any other phases in samples. The SEM images exhibit that the surface structure of the primary particles is clearly improved. The measurement of electrochemical performance shows that the cycle ability and the first discharge capacity are also improved with the doping of lithium