Spherical Li3V2(PO4)3/C(LVP/C) composites were synthesized by sol–gel method using diethylene glycol as the spheroidizing medium and glucose as the carbon source. The crystal structure, morphology, the lithium diffusion behavior and high rates capacities were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), X-ray photoelectron spectroscopy (XPS) and electrochemical methods. Results indicated that the sphere-like LVP/C sample prepared with 10wt% glucose has a uniform carbon layer about 10nm on the surfaces, and presented a high discharge capacity of 131.8, 126.5, 102.4, 82.8mAhg−1 at 0.1, 2, 10, 20C between 3.0 and 4.3V with no obvious capacity fading during 200 cycles at the rate of 2C. While in the voltage region of 3.0–4.8V, it owned the largest reversible capacity of 169.4, 139.8, 121.7mAhg−1 at 0.5, 1, 5C, respectively. Its capacity retained 79.9% after 200 cycles at 2C, and the apparent Li-ion diffusion coefficient was calculated to be 3.37×10−9 cm2 s−1.