We investigated the electrochemical characteristics of LiFePO4 when used as the cathode material for rechargeable lithium batteries. We also studied the change in the crystal structure of the material during discharge. The material prepared at a relatively low temperature of 675°C showed a higher charge and discharge capacity than that prepared at higher temperatures. This was because material prepared at a low temperature has a relatively small particle size and a rough surface morphology. We also found that the crystal structure of electrochemically delithiated LiFePO4 was similar to a heterosite structure and the sample reverted to its original triphylite structure after electrochemical lithiation.