A series of V-doped LiFePO4/C composites are synthesized through a quasi-sol-gel method using organophosphorus source. Amino tris(methylene phosphonic acid) is utilized as phosphorus and carbon co-precursor, sucrose as assisted carbon source, and NH4VO3 as dopant. The effect of vanadium doping on the structural property and electrochemical performance of LiFePO4/C cathode material is systematically investigated. Carbon is coated uniformly on the LiFePO4 nanoparticles and vanadium (+ 4) is incorporated into LiFePO4/C without altering the olivine structure. The appropriate V-doping refined LiFePO4 particle size, induced the lattice distortion and weakened the Li-O bonds, leading to the enhancement of Li+ diffusion and electronic conductivity, and hence resulting in the improvement of the electrochemical performance of LiFePO4/C composites. A high rate discharge capacity of 140.2 mAh g (1) at 5 C, 120.4 mAh g (1) at 10 C, and 105.8 mAh g (1) at 20 C is obtained for LiFe0.97V0.03PO4/C. It is demonstrated that the simple and green synthesis process of the quasi-sol-gel route with organophosphonic acid as precursor is efficient to fabricate V-doped LiFePO4/C composite cathode materials for high-power lithium-ion batteries. (C) 2015 Elsevier Ltd. All rights reserved.