A novel catalyst of copper hydroxyphosphate (Cu-2(OH)PO4) that has neither microporous nor mesoporous pores was successfully synthesized by a hydrothermal method. Catalytic data in the hydroxylation of phenol, benzene and naphthol by hydrogen peroxide showed that copper hydroxyphosphate is a very active catalyst. Comparison of various catalysts on phenol hydroxylation suggests that the unusual catalytic activity on the Cu-2(OH)PO4 catalyst may be dependent on the unique structure of as-synthesized Cu-2(OH)PO4. Characterization of catalytic phenol hydroxylation over Cu-2(OH)PO4 catalyst by electron spin resonance (ESR) gives very strong signals assigned to hydroxyl radical ( OH) species, the intensities of which are linearly related to the catalytic conversion, suggesting that hydroxyl radicals are important intermediates in the catalysis.