Pure olive-type phased LiFePO4 powders were successfully synthesized b y hydrothermal processes. The samples were investigated by X-ray diffraction, sc anning electron microscopy and so on. Results showed that hydrothermal product w ere of pure olive-type phase with a relatively smaller particle size and regular er morphology compared with the products prepared by solid-state reaction and ba ll milling activation approaches. Charge/discharge curves at 0.5 C rate revealed that the hydrothermal products had a first discharge capacity of 124 mAh·g-1, and the capacity fading rate was only 10.7% after 50 cycles.