A method for preparation of alkoxy-amine hydrochloride, comprising the following steps: feeding a ketone compound, hydrogen peroxide, water, and ammonia into a reactor for contact reaction under the conditions of oximation reaction of ketone and ammonia, in the presence of a titanium-silicon molecular sieve catalyst, to prepare ketoxime compound, wherein, the molar ratio of the hydrogen peroxide to the ketone compound is 0.1 or more and less than 1; allowing the ketoxime compound obtained in step to have contact reaction with a halohydrocarbon under the conditions of substitution reaction, and separating ketoxime ether compound from the product of the contact reaction; feeding the ketoxime ether compound obtained in step and hydrochloric acid solution respectively into a second rectification tower continuously for catalytic distillation, and separating alkoxy-amine hydrochloride from the liquid at the tower bottom of the second rectification, tower, wherein the process for feeding the ketoxime ether compound obtained in step and the hydrochloric acid solution respectively into the second rectification tower continuously comprises: feeding the ketoxime ether compound obtained in step into the second rectification tower through a first feed inlet, and feeding the hydrochloric acid solution into the second rectification tower through a second feed inlet, wherein, the number of plates or the theoretical plate number D1 from the first feed inlet to the tower bottom and the number of plates or the theoretical plate number D2 from the second feed inlet to the tower bottom is 30-80% of the total number of plates or the theoretical plate number of the second rectification tower respectively, and D1<D2. feeding a ketone compound, hydrogen peroxide, water, and ammonia into a reactor for contact reaction under the conditions of oximation reaction of ketone and ammonia, in the presence of a titanium-silicon molecular sieve catalyst, to prepare ketoxime compound, wherein, the molar ratio of the hydrogen peroxide to the ketone compound is 0.1 or more and less than 1; allowing the ketoxime compound obtained in step to have contact reaction with a halohydrocarbon under the conditions of substitution reaction, and separating ketoxime ether compound from the product of the contact reaction; feeding the ketoxime ether compound obtained in step and hydrochloric acid solution respectively into a second rectification tower continuously for catalytic distillation, and separating alkoxy-amine hydrochloride from the liquid at the tower bottom of the second rectification, tower, wherein the process for feeding the ketoxime ether compound obtained in step and the hydrochloric acid solution respectively into the second rectification tower continuously comprises: feeding the ketoxime ether compound obtained in step into the second rectification tower through a first feed inlet, and feeding the hydrochloric acid solution into the second rectification tower through a second feed inlet, wherein, the number of plates or the theoretical plate number D1 from the first feed inlet to the tower bottom and the number of plates or the theoretical plate number D2 from the second feed inlet to the tower bottom is 30-80% of the total number of plates or the theoretical plate number of the second rectification tower respectively, and D1<D2.