Li3V2(PO4)3/C composite material has been firstly synthesized via a sol–gel method based on the composite chelating reagents of glycine and beta-cyclodextrin. The product is investigated by X-ray diffraction (XRD), scanning electron microscope (SEM), high-resolution transmission electron microscopy (HR-TEM) and electrochemical method. In the range of 3.0–4.3V, the LVP/C electrode presents excellent cyclic performance at high discharge rates. The largest capacities of 87.1, 89.9 and 74.5mAhg−1 are delivered at 0.9C charge and 35C discharge rates, 0.7C charge and 40C discharge rates, 0.6C charge and 50C discharge rates, respectively. 86.8%, 89.7% and 90.8% of the largest values are retained for the LVP/C electrode at the three discharge rates in the 500th, 300th and 250th cycles, respectively. The unexceptionable high-rate and cyclic performance is attributed to the existence of the composite carbon sources and the small particle size of the Li3V2(PO4)3/C.