The electrochemical properties of LiFePO4 as a cathode of lithium ion batteries considerably depend on a particle size of LiFePO4 and a condition of carbon coating. In this study, LiFePO4 powders were prepared using ultrasonic spray pyrolysis method, and then LiFePO4/C composites were made by infiltrating sucrose solution into LiFePO4 powders, drying, high-energy milling and annealing. The effects of high-energy milling were analyzed by comparing with electrochemical properties of powders synthesized without high-energy milling. It was found that the milling process drastically reduced the particle size of synthesized powders and electrical conductivity, and improved discharge capacity, cycle stability and rate performance.