V-doped LiFePO4/C cathode materials were prepared through a carbothermal reduction route. The microstructure was characterized by X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The electrochemical Li+ intercalation performances of V-doped LiFePO4/C were compared with those of undoped one through galvanostatic intermittent titration technique, cyclic voltamperometry, and electrochemical impedance spectrum. V-doped LiFePO4/C showed a high discharge capacity of ∼70mAhg−1 at the rate of 20C (3400mAg−1) at room temperature. The significantly improved high-rate charge/discharge capacity is attributed to the increase of Li+ ion “effective” diffusion capability.