Abstract: Rare earth composite solid superacid SO₄^2-/ZrO_2^- 2%Gd₂O₃ are prepared, the catalyst has high catalytic activity in the synthesis of n-amyl acetate. The factors influencing the reaction are investigated. The results show that the optimum reaction conditions are as follows: the mol ratio of amyl alcohol to acetic acid is 1:1.5, the use level of SO₄^2-/ZrO_2^- 2%Gd₂O₃ is 6% of the mass of amyl alcohol, the reaction temperature is 130℃ and the reaction time is 6h, the esterification yield of n-amyl acetate can reach 98.93%, its reaction preference can reach 100%. The catalyst has good reusability, it can be activated and revivified.