The invention relates to a method for synthesizing n-butyl acetate through ester exchange, and concretely relates to a method for synthesizing n-butyl acetate through ester exchange. The method adoptsa multifunctional composite alkaline material catalyst to directly catalyze in order to synthesize n-butyl acetate and methanol. Azeotropic separation is carried out while reaction rectification without extracting or separating the product by a solvent, so the routine process flow for synthesizing the n-butyl acetate is greatly simplified, multiple components can be separated at one time, and theseparation purity is high. The reaction raw material is an excess methyl acetate and n-butanol mixture, methyl acetate and n-butanol enter a T1 first reaction rectifying tower together, the n-butanolis completely reacted, and the final products are the n-butyl acetate and methanol. The method has the advantages of cleanness, high efficiency and no pollution in the whole reaction process, and nowastes.