Liquid-phase cyclohexanone ammoximation over TS-1 was carried out in a continuous flow microreactor with ultrasound, which can maintain the stability of the dispersion of catalysis. The influence of temperature, catalyst amount and reactant concentrations was investigated, while the selectivity reached up to higher than 99%. A kinetic equation for ammoximation rates was developed, which was faster than previous work in a batch reactor. Enhanced mass transfer in microreactors and ultrasound field plays a key role in the kinetic measurements, so that the kinetics is much closer to the intrinsic kinetics. According to the kinetic equation, we predict the chemical reaction mechanism with an intermediate of hydroxylamine. Experiments show that the continuous flow microreactor with ultrasound is a good research platform of nano-catalysis reactions.