Abstract: The octyl hexanoate was synthesized by hexanoic acid and octanol, using solid superacid SO42-/SnO2-Al2O3as catalyst. The effect of esterification conditions on the esterification rate were investigated, and the product were characterized by GC-MS and FTIR. Through the orthogonal experiment, the optimized synthesis of octyl hexanoate was obtained:the molar ratio of hexanoic acid to octanol was 1∶1.5, amount of catalyst was0.45g (relative to 0.05mol hexanoic acid) , cyclohexane dosage was 3mL, and reaction time was 1.5h, under this condition, the esterification rate could achieve 98.04%.