Non-stoichiometric compound fluoride-doped LiFePO4/C cathode materials were synthesized via solid-state reaction using MgF2 and AlF3 as dopant. The fluoride-doped LiFePO4/C samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electrochemical testing. The results show that the materials are well crystallized and fluoride doping cannot change the space structure of LiFePO4. Slight amounts of Fe2O3 with no fluoride impurity were detected. Charge-discharge curves show that fluoride-doped samples have higher capacity at low rates compared with undoped LiFePO4/C. AlF3-doped samples have highest capacity at high discharge current. Both doped samples have larger polarization voltage than undoped samples. All samples exhibit good cycle stability. Non-stoichiometric compound fluoride-doped LiFePO4 / C cathode materials were synthesized via solid-state reaction using MgF2 and AlF3 as dopant. The fluoride-doped LiFePO4 / C samples were characterized by X-ray diffraction (XRD) ), transmission electron microscopy (TEM), and electrochemical testing. The results show that the materials are well crystallized and fluoride doping can not change the space structure of LiFePO4. Slight amounts of Fe2O3 with no fluoride impurity were detected. Charge-discharge curves show that fluoride-doped samples have higher capacity at low rates compared with undoped LiFePO4 / C. AlF3-doped samples have highest capacity at high discharge current. Both samples have larger polarization voltage than undoped samples. All samples exhibit good cycle stability.