The inevitably low value of glycerol has led to extensive investigations on glycerol conversion to value-added derivatives. The esterification of glycerol with oleic acid is currently a very important industrial process. In this work, a novel heterogeneous acid catalyst featuring hydrophobic surface is developed on modified ZrO2-SiO2 support as water-tolerant solid acid catalyst is vital for biphasic esterification reactions that produce water. The novel ZrO2-SiO2-Me&Et-PhSO3H catalyst was prepared through silication and surface modification with trimethoxymethylsilane and 2-(4-chlorosulfonylphenyl)ethyltrimethoxysilane. This work showed that it is possible to control the acidity and hydrophobicity of the catalyst by tailoring the amount of surface modification agents. It was found that the hydrophobicity of the catalyst decreased as its acidity increased. Furthermore, at constant catalyst acidity, the more hydrophobic catalyst showed a better yield.