Serrabrancaite (MnPO 4 ·H 2 O) was synthesized by oxidizing Mn(H 2 PO 4 ) 2 with NaClO solution using a refluxing process at atmospheric pressure, and a mixed solution of MnCl 2 and H 3 PO 4 could substitute for Mn(H 2 PO 4 ) 2 in the process. The products were characterized by X-ray diffraction, Fourier transform infrared spectroscopy and scanning electron microscopy. Hureaulite was formed when single solution of Mn(H 2 PO 4 ) 2 was refluxed for 12 h at 60 °C. Rodlike hureaulite was fabricated by refluxing reaction of 30 mmol Mn(H 2 PO 4 ) 2 and 60 mmol NaClO solution with adding hydrochloric acid within 40 mmol. Granular hureaulite was formed by refluxing of 30 mmol MnCl 2 and 60 mmol NaClO solution with adding phosphoric acid within 30 mmol. For the two above-mentioned reaction systems, MnPO 4 ·H 2 O was prepared by adding hydrochloric acid no less than 80 mmol and phosphoric acid no less than 60 mmol respectively. MnPO 4 ·H 2 O yield increased with elevating reflux temperature, and increased firstly and then decreased with increasing additional amount of acid. The highest recovery yield of MnPO 4 ·H 2 O reached 84.1% when Mn(H 2 PO 4 ) 2 was performed as bivalent manganese source, and approached 74.0% when MnCl 2 and H 3 PO 4 were used instead.