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 10 wt% glucose has a uniform carbon layer about 10 nm on the surfaces, and presented a high discharge capacity of 131.8, 126.5, 102.4, 82.8 mAh g(-1) at 0.1, 2, 10, 20C between 3.0 and 4.3 V with no obvious capacity fading during 200 cycles at the rate of 2 C. While in the voltage region of 3.0-4.8V, it owned the largest reversible capacity of 169.4, 139.8, 121.7 mAhg(-1) at 0.5, 1, 5 C, respectively. Its capacity retained 79.9% after 200 cycles at 2 C, and the apparent Li-ion diffusion coefficient was calculated to be 3.37 x 10(-9) cm(2) s(-1). (c) 2013 Elsevier Ltd. All rights reserved.