Spherical LiFePO4/C precursor powders were successfully prepared by spray pyrolysis. Various types of organic compounds such as glycolic acid, malic acid, citric acid, fructose and sucrose were used as carbon sources. X-ray diffraction analysis revealed that the olivine phase was obtained by calcining over 600 °C under an argon (95%)/hydrogen (5%) atmosphere. The particles exhibited a spherical morphology with approximately 1.5 μm. LiFePO4/C cathode derived from sucrose exhibited higher rechargeable capacity and cycle stability. The rechargeable capacity of LiFePO4/C cathode was approximately 154 mAh/g at 1 C. 90% of initial discharge capacity was maintained after 100 cycles.