LiFePO4/C composite cathode materials were synthesized by one-step solid-state reaction using FePO4 as main raw materials and solid PVA (Polyvinyl Alcohol) as a reductive agent and carbon source. The sample was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), particle size analysis and charge-discharge test. The results indicated that the carbon generated from the pyrogenation of PVA did not affect the olivine structure of the cathode materials but considerably improved its high-rate discharge ability and cycle performance. The initial discharge capacity of the sample was 149.7, 133.1, 120.6, 93.0 mAh/g at 0.2C, 1C, 2C, 5C respectively, and the discharge capacity could reach 90 mAh/g at 5C rates after 80 cycles. It is believed that the carbon coating could lead to small particle size and high electronic conductivity of active materials, thus leading to excellent electrochemical performance of LiFePO4/C cathode materials.