The use of methyl acetate instead of methanol for supercritical synthesis of glycerol-free biodiesel from vegetable oils is a new process and its study is very limited in the literature. In this work, it has been tested for the first time on three edible and non-edible oils with different fatty acid composition. The process was also applied to waste oil with higher free fatty acid (FFA) content. The results demonstrate that the oil composition does not significantly influence the biodiesel yield. The influence of temperature, pressure and molar ratio of reactants was studied. All the oils achieved complete conversion after 50 min at 345 degrees C, 20 MPa with methyl acetate: oil molar ratio equal to 42:1. The obtained data also allowed calculating the apparent rate coefficients and activation energies. Eventually, some new information on the process was obtained. Thermal degradation of triacetin, which substitutes glycerol as the by-product of the transesterification reaction, was observed. Some indicative experiments were performed to understand the role of the acetic acid produced by FFA esterification. (C) 2010 Elsevier Ltd. All rights reserved.