Complex rare earth solid acid catalyst SO42-/C-TiO2-CeO2 was prepared using high temperature sulfonation.The catalytic performance of the catalyst was evaluated by esterification reaction of oil acid and methanol as a probe reaction and the influence of catalytic activity such as the content of the rare earth CeO2,sulfonation temperature and sulfonation time was studied.The results showed that the catalyst SO42-/C-TiO2-CeO2 was prepared under the best preparation conditions of the rare earth CeO2 mol percentage of 2%,the sulfonation temperature of 200℃ and sulfonation time of 10h,under these conditions,the catalytic esterification rate of waste oil with methanol esterification was highest and reached 94.78%.The catalyst was characterized by FTIR,XRD,SEM,DTG and X-ray fluorescence,which shows that the rare earth oxide CeO2 and metal oxide TiO2 cured SO42- role in common, promoted SO42- with bidentate structure, enhanced catalytic activity and improved the stability of the catalyst SO42- /C-TiO2-CeO2.