Nano LiFePO4/C particles with high capacity and high rate were fabricated by one-step solid-state reaction using nano Fe2O3, LiH2PO4 and sucrose as raw materials. The effect of synthesis temperature on the morphology and the electrochemical performance was investigated. LiFePO4/C materials were characterized by differential scanning calorimetry (DSC) and thermogravimetry (TG), X-ray diffraction (XRD), X-ray photoelectron spectrometry (XPS), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and the elemental analyzer. The results show that nano Fe2O3 can reduce and make uniform the LiFePO4 grain size (<100nm) effectively as well as accelerate the solid-state reaction kinetics which is a convenient way for industrialization. The precursor sintered at 740°C for 5h exhibits the highest electrochemical capacity (166.9mAh/g at 0.1C) and the best rate performance.