The ammoximation of acetophenone to acetophenone oxime with 28%(ω) H2O2 over TS-1 molecular sieve catalyst was studied. The influences of various parameters such as solvent, temperature, auxiliary catalyst (alumina and ammonium acetate), molar ratios of NH3 to acetophenone and H2O2 to acetophenone on the reaction were investigated. The results show that the best solvent is ethanol and the optimal reaction temperature 80℃, and ammonium acetate can promote the formation of acetophenone oxime. In order to achieve the high yield, the molar ratios of NH3 to acetophenone and H2O2 to acetophenone should be kept above 2.00 and 1.27, respectively.