In this paper, hydrothermal method was conducted to synthesize LiFePO4 raw material. Carbon and TiO2 hybrid coating was prepared on the surface of LiFePO4 through sol-gel method, the tiny TiO2 particles were dispersed homogeneously on the surface and its size is about 2-4 nm. The rate performance testing proved that appropriate content TiO2 in the hybrid coating could obviously improve the rate performance of LiFePO4. The samples with 0.2 wt% (nominal) TiO2 particles in the hybrid coating owned the optimal rate performance at 0.5C, 1C, 3C and 5C, respectively. The reason was that TiO2 particles enlarged the interface in coating layer. This hybrid structure can provide more reaction sites for Li+ ion insertion/extraction. Another advantage of this carbon and TiO2 hybrid coating is that it does not need to strictly limit the content of carbon in the coating, which is very useful for scale production of carbon coating process for LiFePO4.