LiCoPO4 was prepared by a citric acid assisted sol-gel method and exploited as cathode material for lithium ion batteries. TG curve showed the appropriate temperature of the reaction and X-ray diffraction patterns indicated that LiCoPO4 synthesized at different temperatures was crystallized in an orthorhombic structure. During charge-discharge cycles, LiCoPO4 presented a plateaus of 4.8V corresponding to Co3+/Co2+ redox couples, and a discharge capacity of 126.3 mAh/g in the first cycle. The CV curve of LiCoPO4 showed that Li-ion diffusion in LiCoPO4 obeyed a different mechanism between charge and discharge processes.