A series of Mo-doped LiFe1-3xMoxPO4/C (x = 0.000, 0.025, 0.050, 0.100, 0.150) cathode materials are synthesized by sol-gel method. XRD, ICP and Rietveld refinement results reveal that Mo doped in the crystal lattice and probably occupied Fe site. The structure benefits the transportation of Li+ and the diffusion of Li+ in the doped materials are enhanced remarkably than that of the undoped one, which leads to excellent electrochemical performance. The doped sample with x = 0.025 exhibits the best electrochemical performance, with the initial discharge capacity of 162.3 mAh g(-1) at 0.1 C rate. (C) 2011 Elsevier Ltd. All rights reserved.