The present invention discloses one kind of catalyst for hydroxylating benzene to synthesize phenol and its application method. The catalyst with molecular sieve as carrier is prepared through soaking the carrier to support salt of transition metal, roasting, mixing with phthalic anhydride, urea and ammonium molybdenate, and in-situ solid phase synthesis. It is used in the oxidation of benzene dissolved in solvent comprising acetic acid and water with oxygen as oxidant in the presence of reductant ascorbic acid to synthesize phenol. The catalyst of the present invention has no loss of active components, easy separation from the reaction system, mild reaction condition, high yield of target product phenol and other advantages.