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Lithium-ion battery cathode materials Li2.5Na0.5V2(PO4)3/C and Li3V2(PO4)3/C were prepared by sol-gel method.The XRD pattern of composite material Li2.5Na0.5V2(PO4)3/C fits well to β-Li3V2(PO4)3’s,which prove that the monoclinic structure has changed to rhombohedral structure accompany with Li+ was replace by Na+; Electrochemical test results show that,compared to Li3V2(PO4)3/C,the charge-discharge voltage plateau of Li2.5Na0.5V2(PO4)3/C does become more smooth.