The effect of the precipitator (NaOH, NH4OH) and the amount of the precipitator (150, 200, 250, 300 ml) on the formation of Fe3(PO4)2, which is the precursor used for cathode material LiFePO4 in Li-ion rechargeable batteries was investigated by the co-precipitation method. A pure precursor of olivine LiFePO4 was successfully prepared with coprecipitation from an aqueous solution containing trivalent iron ions. The acid solution was prepared by mixing 150 ml FeSO4(1M) and 100 ml H3PO4(1M). The concentration of the NaOH and NH4OH solution was 1 M. The reaction temperature (25oC) and reaction time (30 min) were fixed. Nitrogen gas (500 ml/min) was flowed during the reaction to prevent oxidation of Fe2+. Single phase Fe3(PO4)2 was formed when 150, 200, 250 and 300 ml NaOH solutions were added and 150, 200 ml NH4OH solutions were added. However, Fe3(PO4)2 and NH4FePO4 were formed when 250 and 300 ml NH4OH was added. The morphology of the Fe3(PO4)2 changed according to the pH. Plate-like lenticular shaped Fe3(PO4)2 formed in the acidic solution below pH 5 and plate-like rhombus shaped Fe3(PO4)2 formed around pH 9. For the NH4OH, the pH value after 30 min reaction was higher with the same amount of additions of NaOH and NH4OH. It is believed that the formation mechanism of Fe3(PO4)2 is quite different between NaOH and NH4OH. Further investigation on this mechanism is needed. The prepared samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and the pH value was measured by pH-Meter.