The invention relates to a method for synthesizing an oxime ether compound based on C-N bond breakage. The method comprises the step of making a compound shown in equation (1) and a compound show in equation (2) react in the presence of peroxide and an organic solvent to obtain the oxime ether compound as shown in formula (3), and reaction expression is shown in the description. According to the method, synthesis path is short, starting materials are simple, reaction condition is mild, the peroxide is cheap and free of pollution, substrate range is wide, products are easy to separate, and adaptability is high when reaction is amplified to be at the gram grade.