A Li3V2(PO4)3/C (LVP/C) electrode and a new Li3V2(PO4)3/C electrode using LiCoO2 as an additive (LVP/LCO/C) have been successfully fabricated and investigated via physical and electrochemical methods. Compared with the LVP/C electrode, the LVP/LCO/C electrode presents better rate capability and cyclic performance in the range 3.0–4.3V. For the LVP/LCO/C electrode, the largest capacities of 99.3 and 68.0mAhg−1 are delivered at 1 and 15C charge rates and 51C discharge rate, respectively. 80.4% of the largest value is kept at 1C charge and 51C discharge rates in the 800th cycle. The excellent rate capability and cyclic performance are attributed to the small crystallite size of LVP particles, the small particles, narrow particle size distribution in the LVP/LCO/C electrode, large specific surface area and pore size, low electrical resistance for the LVP/LCO/C electrode, and the existence of the other electroactive LCO.