The carbon-coated monoclinic Li3V2(PO4)3/C composite was prepared via rheological phase method with EDTA (ethylene diamine tetraacetic acid), a new type of carbon source. XRD patterns demonstrate the pure monoclinic structure of the sample. The images of SEM show the uniform and optimized particles size, which greatly improves the electrochemical performance. The TEM test shows the amorphous carbon around the surface of the particles. In the potential range of 3.0–4.3V, the initial discharge capacity is 129.1mAh/g at 0.1C which is almost near the theoretical capacity, and it keeps so fairly stable that a discharge capacity of more than 125mAh/g can still be held after 50 galvanostatical cycles. It also exhibits an excellent rate capability with high discharge capacities of more than 108mAh/g at 2C after 100cycles.