A modified solid-state method was used to prepare LiFePO4. With the aid of deionized water, a mixture containing Fe2O3, NH4H2PO4 (or (NH4)2HPO4), LiOH, glucose and oxalic acid was prepared into fluffy powders, which were heated in a carbon-coated crucible at 700 degrees C for 3 hours to synthesize LiFePO4 without any inert gas flow. For the first time, the roles of NH4H2PO4 and (NH4)2HPO4 on the preparation of LiFePO4 were systematically investigated. The obtained samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM) and energy dispersive spectroscopy (EDS), revealing that the crystallinity of the LiFePO4 sample prepared from NH4H2PO4 is superior to that prepared from (NH4)2HPO4 and the particle size of the sample prepared from NH4H2PO4 is smaller than that prepared from (NH4)2HPO4. The specific capacity, cycle property and rate capabilities were also compared between the as-prepared LiFePO4 samples. A better electrochemical performance was observed in the sample prepared from NH4H2PO4.