In this study, the catalytic performance of commercial CaO modified by trimethylchlorosilane (TMCS) for transesterification of rapeseed oil and methanol to biodiesel production was investigated. It was found that the fatty acid methyl esters (FAME) yield of the modified CaO was greatly enhanced from 85.4% to 94.6%. The possible reason lies on promoting the absorption of grease to CaO surface. Good results of repeated experiments showed that the modified catalyst has the capacity of water resistance and can be reused for several runs without significant deactivation, which can be confirmed by the humidity test in the vapor-saturated atmosphere. Both the characterizations of the catalyst and the effects of various factors such as mass ratio of catalyst to oil, reaction temperature and molar ratio of methanol to oil were investigated. (C) 2011 Elsevier Ltd. All rights reserved.