The invention discloses a method for preparing an imine compound from alcohol and amine through catalytic oxidation. According to the method, an alcohol compound and an amine compound are used as reaction substrates, and a feeding mol ratio of the alcohol compound to the amine compound is 100: 100-60; 9-azabicyclo[3.3.1]nonane N-oxyl free radical is used as a catalyst, potassium hydroxide is used as an auxiliary agent, and a feeding mol ratio of the amine compound to the 9-azabicyclo[3.3.1]nonane N-oxyl free radical to potassium hydroxide is 100: 1-6: 10-50; air is used as an oxidizing agent, the reaction substrates are added into an organic solvent, and the mass of the used organic solvent is 2.5 to 5 times of the reaction substrate the amine compound; and a reaction is carried out at normal pressure at a temperature of 70 to 110 DEG C for 2 to 12 h, and aftertreatment is carried out after completion of the reaction so as to obtain the imine compound. The method provided by the invention is simple and safe to operate, reduces environmental cost due to usage of clean oxygen as the oxidizing agent and prevents the problem of transition-metal pollution by discarding usage of any transition-metal catalyst.