Li 3 V 2 (PO 4 ) 3 /Cu composite cathode material was prepared via sol–gel method by adding of 1.8wt% Cu powder into the precursor solution. The structural and physical properties, as well as the electrochemical performance of the material were compared with those of Cu-free Li 3 V 2 (PO 4 ) 3 . X-ray diffraction showed that Cu did not enter the crystal structure of Li 3 V 2 (PO 4 ) 3 . The Li 3 V 2 (PO 4 ) 3 /Cu composite material had a higher electronic conductivity comparing with that of Cu-free Li 3 V 2 (PO 4 ) 3 . Electrochemical impedance spectroscopy showed that the adding of Cu decreased the charge transfer resistance of the electrode. In addition, the lithium diffusion coefficient was prominently enhanced from 1.3×10 −9 to 2.8×10 −8 cm 2 s −1 . Based on the these advantages, the Li 3 V 2 (PO 4 ) 3 /Cu composite material exhibited much better cycling performance than the Cu-free Li 3 V 2 (PO 4 ) 3 .