The effect of fluorine doping on the electrochemical performance of LiFePO4/C cathode material is investigated. The stoichiometric proportion of LiFe(PO4)(1-x) F-3x /C (x = 0.01, 0.05, 0.1, 0.2) materials was synthesized by a solid-state carbothermal reduction route at 650 A degrees C using NH4F as dopant. X-ray diffraction, scanning electron microscope, energy-dispersive X-ray, and X-ray photoelectron spectroscopy analyses demonstrate that fluorine can be incorporated into LiFePO4/C without altering the olivine structure, but slightly changing the lattice parameters and having little effect on the particle sizes. However, heavy fluorine doping can bring in impurities. Fluorine doping in LiFePO4/C results in good reversible capacity and rate capability. LiFe(PO4)(0.95) F-0.15/C exhibits highest initial capacity and best rate performance. Its discharge capacities at 0.1 and 5 C rates are 156.1 and 119.1 mAh g(-1), respectively. LiFe(PO4)(0.95) F-0.15/C also presents an obviously better cycle life than the other samples. We attribute the improvement of the electrochemical performance to the smaller charge transfer resistance (R (ct)) and influence of fluorine on the PO (4) (3-) polyanion in LiFePO4/C.