The invention discloses an oximation method of ketone to improve the oximation reaction efficiency and selectivity. Compared with a conventional ammoximation process, the oximation method first adoptsa reactive distillation process, in the presence of a novel magnetic modified titanium-silicon molecular sieve, hydrogen peroxide reacts with ammonia to produce hydroxylamine, a hydroxylamine aqueoussolution with high concentration is obtained by distillation and concentration, and the hydroxylamine aqueous solution and ketone are subjected to an oximation reaction to obtain ketoxime. Under theprocess conditions, the ketone and the hydroxylamine adopt a continuous oximation process. Moreover, since the concentration of the hydroxylamine is increased, the efficiency is significantly improved, and the removal of the ammonia also makes the selectivity of the ketoxime as high as 99.8%.