Phospho-olivine LiFePO4 has been prepared using a facile hydrothermal method by optimizing the reaction temperatures. Structural and morphological properties of the as-prepared LiFePO4 powders are systematically characterized using X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, infrared spectra, UV-vis spectra, and Mossbauer spectroscopy. It is demonstrated that the samples prepared in the temperature range from 160 to 200℃ crystallize in a single phase of phospho-olivine structure. All particles are rod-like, showing dimensions of approximately 150-200 nm in width and 500-600 nm in length with a preferential growth direction of [001]. Within the lattice of LiFePO4 rods, Fe2＋ ions partially disorderly occupy the Li＋ sites, which increases the cell volume. The electrochemical performance of LiFePO4 is investigated by charge/discharge experiments. It is found that LiFePO4 rods prepared at 200℃ deliver a specific discharge capacity of 147 mAh g-1, which is apparently superior to those prepared at lower reaction temperatures like 160 and 180 ℃This observation is explained in terms of the thinner surface noncrystalline layer and lower level of Fe2＋ disorderly occupying the Li＋ sites.
