Acidic ionic liquid([BsAIm][OTf]) was immobilized on sulfhydryl-group-modified SiO2(MPS-SiO2) via free radical addition reaction. The[BsAIm][OTf] loading on acidic ionic liquid-functionalized silica([BsAIm][OTf]/SiO2) was controlled through tuning the sulfydryl(SH)content of MPS-SiO2. All the samples were characterized by FT-IR, elemental analysis, N2adsorption-desorption measurements and TGDTA. The catalytic performance of [BsAIm][OTf]/SiO2in the esterification of oleic acid and the transesterification of glycerol trioleate for biodiesel production was investigated. The results showed that with the increase of [BsAIm][OTf] loading on SiO2the specific surface area and pore volume of [BsAIm][OTf]/SiO2decreased, and the pore diameter of [BsAIm][OTf]/SiO2narrowed. In the esterificaiton of oleic acid, the oleic acid conversion increased with the increasing [BsAIm][OTf] loading. In the transesterification of glycerol trioleate, with the increasing[BsAIm][OTf] loading the glycerol trioleate conversion decreased and the selectivities to glycerol monooleate and methyl oleate increased.