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 LiO 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 140.2mAhg−1 at 5C, 120.4mAhg−1 at 10C, and 105.8mAhg−1 at 20C 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.