Ga2O3/palygorskite composite catalyst was prepared by an impregnation method with palygorskite loading gallium oxide(Ga2O3), the structure of catalyst was characterized by means of IR, XRD, BET and TEM. The preparation conditions and catalytic activity of catalyst were investigated. The results indicated that the suitable preparation conditions of catalyst were Ga2O3 loading at 10 %, and calcination temperature 450 ℃. The average esterification rate was 95.0 % under the following conditions for synthesis of cyclohexyl cinanmate: n(cinnamic aicd):n(cyclohexanol)=1:4.5(cinnamic aicd was 0.02 mol), catalyst amount was 0.5 g, heat at 130 ℃ for 70 min. It could reach to 81.5 % while used for 5 times. It's a second-order reaction, the apparent activation energy was 90.78 kJ/mol, and the reaction rate constant was 1.03×10-2 L/(mol•min) in 130 ℃.