The invention discloses an ester ammonolysis reaction catalyst composition and a preparation method of L-menthane carboxamide. The ester ammonolysis reaction catalyst comprises a catalyst and a ligand, wherein the catalyst is cuprous salt CuX, the ligand is a (R)-N, N, N, N-tetraalkyl binaphthylamine compound shown as the specification, wherein R1, R2, R3 and R4 are independently selected from thegroups shown as the specification. Menthyl chloride is used as the starting raw material in the method to react with metal magnesium to prepare menthyl magnesium chloride, then reaction with chloroformate with different substituent groups is carried out to obtain menthyl formate, and then ammonolysis under the catalysis of an ester ammonolysis catalyst composition is conducted to obtain the L-menthane carboxamide. The yield is improved, the production cost is reduced, the optical purity is high, and environmental protection and no wastewater discharge are realized.