From the perspective of energy saving, green and environmental protection, the solid superacid (SO42-/TiO2) was used as the catalyst to prepare chloroacetic acid high-carbon fatty alcohol ester, using the orthogonal test method, taking the esterification rate as the investigation index, the influence of five factors on the reaction was investigated, and the order of the influence was as follows: reaction time> amount of water agent> material ratio>catalyst dosage> reaction temperature, and the better reaction conditions were obtained: reaction temperature 5 °C, reaction time 110.5 h. The material ratio was 5:1.1 (n solution: n acid), the catalyst dosage was 157%, the amount of aqueous agent was 4 mL, and the esterification rate reached 30.87%.The activity and reproducibility of the solid superacid catalyst were investigated, and the results showed that the activity and reproducibility of the synthesis of chloroacetic acid high-carbon fatty alcohol ester catalyzed by this solid superacid were good.