A series of Mo-doped LiFe1−3x Mo x PO4/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 162.3mAhg−1 at 0.1C rate.