The invention discloses a method for preparing p-benzenediol and o-benzenediol through the hydroxylation of phenol, which is characterized in that the phenol, oxygen, hydrogen, dilution gas, a solvent and a catalyst are mixed, contacted and reacted under the conditions of the temperature of 0 to 180 DEG C and the pressure of 0.1 to 3.0MPa, the molar ratio of the phenol to the oxygen, the hydrogen and the dilution gas is 1: (0.1 to 10): (0.1 to 10): (0 to 100), the weight ratio of the phenol to the catalyst is (0.5 to 50): 1, the weight ratio of the solvent to the catalyst is (20 to 1000): 1, the catalyst is a microporous titanium silicon material or a composition containing the microporous titanium silicon material, the composition of the microporous titanium silicon material can be represented as follows by using the form of oxides: xTiO2 question mark 100SiO2 question mark yEmOn question mark zE, wherein, the value of x is 0.001 to 50.0, the value of (y plus z) is 0.005 to 20.0 and y/z is less than 1, E refers to one or a plurality of precious metals selected from Ru, Rh, Pd, Re, Os, Ir, Pt and Au, m and n are numbers which are required by the oxidation state of E, and the grain part or all of the material is a hollow structure. The product benzenediol of the method has better selectivity, the conversion rate of the phenol and the effective utilization rate of the hydrogen are higher, and the stable operation cycle is longer.