The invention discloses a solid catalyst for preparation of acetic acid n-butyl ester by an esterification method and the preparation method of the solid catalyst. The invention is characterized in that: ammonia cadmium phosphate is synthesized by using cadmium salt, ammonium phosphate, a diethylenetriamine/ammonium acetate/imidazole/ethylene diamine tetraacetic acid/ammonium oxalate template agent as raw material and by a room-temperature solid phase method. The catalyst prepared by the method has catalytic activity in the preparation process of the acetic acid n-butyl ester by the esterification method, and the esterification ratio can reach about 56 percent. The ammonia cadmium phosphate catalyst synthesized by the room-temperature solid phase method is simple to operate, has no solvent pollution and has the advantages of safety, low cost, low energy consumption, high yield and the like. The esterification reaction for preparing the acetic acid n-butyl ester is mild in condition and convenient to operate; the catalyst is simple to separate; pollution is light; and high popularization and application value is achieved.