Calcium-containing perovskites CaTiO3, CaMnO3, CaZrO3 and Ca2Fe2O5 were synthesized by calcination of mechanochemically treated stoichiometric mixtures of CaCO3 and either TiO2, MnO2, ZrO2 or Fe2O3 powders. X-ray diffraction analysis revealed a pure single perovskite phase for all four samples after calcination. This study proved that the pure perovskite phase exhibited low or no catalytic activity at 60 degrees C for the methanolysis of sunflower oil. However, at 165 degrees C FAME yield of more than 90% was reached after 2 h using CaTiO3, CaMnO3 and CaZrO3 as catalyst. Contrary to inactive pure perovskites at 60 degrees C, the CaTiO3 and Ca2Fe2O5 samples containing a very small amount of "free" CaO also showed methanolysis activity at 60 degrees C. This fact can be used to explain some contradictory statements reported in literature related to the perovskites as catalyst for biodiesel synthesis at mild temperatures. (C) 2015 Elsevier B.V. All rights reserved.