Porous LiFePO4/C microspheres were synthesized by a novel hydrothermal reaction combined with high-temperature calcinations. The morphology of the prepared material was investigated by field-emission scanning electron microscopy. Porous microspheres with diameters around 1-3 microm were obtained, which consisting of primary LiFePO4 nanoparticles. The electrochemical performances of the as-prepared LiFePO4 microspheres were evaluated by cyclic voltammetry, electrochemical impedance spectroscopy and galvanostatic charge-discharge cycling. The carbon coated LiFePO4 microspheres showed lower polarization, higher rate capability, and better cycling stability than that of pristine LiFePO4 microspheres, indicating the potential application as the cathode material for high-power lithium ion batteries.