The methanolysis of sunflower oil was studied in the presence of CaO previously calcined at various temperatures and the optimal temperature for CaO calcination was determined. The sigmoidal process kinetics was explained by the initial triglyceride (TG) mass transfer controlled region, followed by the chemical reaction controlled region in the latter reaction period. The TG mass transfer limitation was due to the small available active specific catalyst surface, which was mainly covered by adsorbed molecules of methanol. In the later phase, the adsorbed methanol concentration decreased, causing the increase of both the available active specific catalyst surface and the TG mass transfer rate, and the chemical reaction rate become smaller than the TG mass transfer rate. (C) 2009 Elsevier Ltd. All rights reserved.