The invention relates to a method for generating hydroxylamine by cyclohexanone-oxime through hydrolyzing. The method comprises the following steps of adding cyclohexanone-oxime, a catalyst and deionized water into a reactor, stirring, refluxing, condensing, and reacting for 0.5 to 2h at the temperature of 15 to 25 DEG C, so as to obtain the hydroxylamine; adding an methylbenzene extracting agent into the reactor, extracting at the reaction temperature, extracting an organic phase from a reaction liquid, and extracting a water phase, so as to obtain a product, namely a hydroxylamine water solution, wherein the catalyst is HZSM-5, silicotungstic acid, phosphotungstic acid or phosphomolybdic acid with a ratio of silicon to aluminum (silicon dioxide/aluminum oxide)) is 25 to 50. The method has the advantages that the reaction conditions are moderate, the operation is simple, the energy consumption is decreased, the environment-friendly and economical meanings are realized, and the environment-friendly catalyzing reaction process is performed.