Phytosteryl oleate synthesized from stigmasterol and oleic acid using the composite catalysts of potassium bisulfate and metal oxide was investigated. By comparing with other sulfates

potassium bisulfate was proved to be more suitable for the esterification of oleic acid and stigmasterol in an efficient and safe way. Taking into account the high catalytic efficiency of metal oxide

the combination of potassium bisulfate and different metal oxides as a kind of composite catalyst may be promising. The catalyst comparative experiments suggested that the composite catalyst of KHSO4-ZnO was the best catalyst in terms of the esterification yields. When the esterification reaction was carried out at 150℃ for 7 h with oleic acid and stigmasterol in a molar ratio of 1.8:1 and 3.0% KHSO4 + 1.0% ZnO catalyst (based on the mass of stigmasterol) under the protection of nitrogen

the highest esterification yield was 92.17%. In the presence of the composite catalyst of KHSO4-ZnO

a new process for the synthesis of stigmasterol oleate with high esterification yield is acquired.