LiFePO4/C cathode material for lithium ion battery was prepared with lithium dihydrogen phosphate, iron oxide, and glucose monohydrate as raw materials. In an attempt to improve the electrochemical performance, the influence of Li:Fe molar ratio was investigated in this paper. Experimental results showed that the best electrochemical performance of LiFePO4/C was reached in this study, when Li:Fe molar ratio was 1.03:1 synthesized preheated ball milling temperature at 300°C for 1h, and then ball milling temperature at 650°C for 8h, at the rates of 0.1, 0.5, 1.0, 2.0, 5.0 and 10C, the initial discharge capacities of 157 (±2), 151 (±2), 144 (±2), 136 (±2), 119 (±2), 102 (±2) mAhg−1, respectively. Moreover, after 50cycles, at rate of 0.1C, the capacity of LiFePO4/C sample was 155 (±2) mAhg−1, and its capacity retention rate achieve 99.5%.