The invention discloses a method for catalyzing ammoximation of cyclohexanone. The method comprises the steps as follows: subjecting cyclohexanone, ammonia, oxygen, hydrogen, diluent gas and a solvent to coming in contact with a catalyst. The mole ratio of cyclohexanone, to ammonia, oxygen, hydrogen and diluent gas is 1:(0.1-10.0):(0.1-10.0):(0.1-10.0):(0-100). The mass ratio of the solvent to the catalyst is (20-1000):1. The catalyst is a microporous titanium-silicon material or a compound containing the microporous titanium-silicon material. The composition of the microporous titanium-silicon material is expressed as xTiO2*100SiO2*yEmOn*zE in an oxide form, wherein x ranges from 0.001 to 50.0; the sum of y plus z ranges from 0.005 to 20.0; the ratio of y to z is smaller than 1; E is one or more metal noble metals selected from Ru, Rh, Pd, Re, Os, Ir, P and Au; m and n are numbers required for meeting the oxidation state of the E; and material grains are partially or totally hollow-structured. The method has the advantages of high selectivity of cyclohexanone oxime, high product activity and stability, environment friendliness and low cost.