Pure, nano-sized LiFePO4 and LiFePO4/C cathode materials are synthesized by spray-drying and post-annealing method. The influence of the sintering temperature and carbon coating on the structure, particle size, morphology and electrochemical performance of LiFePO4 cathode material is investigated. The optimum processing conditions are found to be thermal treatment for 10h at 600°C. Compared with LiFePO4, LiFePO4/C particles are smaller in size due to the inhibition of crystal growth to a great extent by the presence of carbon in the reaction mixture. And that the LiFePO4/C composite coated with 3.81wt.% carbon exhibits the best electrode properties with discharge capacities of 139.4, 137.2, 133.5 and 127.3mAhg−1 at C/5, 1C, 5C and 10C rates, respectively. In addition, it shows excellent cycle stability at different current densities. Even after 50 cycles at the high current density of 10C, a discharge capacity of 117.7mAhg−1 is obtained (92.4% of its initial value) with only a low capacity fading of 0.15% per cycle.