Copper hydroxyphosphate was rapidly synthesized by using a novel hydrothermal method, in which phosphoric acid and copper acetate hydrate are two mainly raw materials in the procedure of preparation without the presence of ethylenediamine. Compared with the conventional method, this new method cost less with less reaction time and without damage to environment. The resultant copper hydroxyphosphate samples were characterized by X-ray diffraction(XRD), single crystal X-ray diffraction and Leica optical microscopy. The as-synthesized samples show significant activities to the hydroxylation of phenol. The exposure of special crystal planes(011) and (101) can be used to explain the high hydroxylation activities of as-synthesized copper hydroxyphosphate at 80 ℃.