The powder mixtures of calcium oxide (CaO) and silica gel (SiO2) in molar ratios of 1:1, 1.5:1, 2:1 and 3:1 were mechanochemically treated with the addition of water, and were subsequently calcined with a goal of synthesizing CaSiO3, Ca3Si2O7, Ca2SiO4 compounds and CaO/Ca2SiO4 two-phase mixture. The prepared materials were characterized by XRD, FTIR, SEM/EDS, particle size laser diffraction (PSLD), UV-vis diffuse reflectance spectroscopy (DRS), N-2 adsorption/desorption isotherms, Hammett indicator for basic strength and volumetric analysis for free CaO content. The catalytic activity of calcium silicates with different Ca/Si ratios was tested in the transesterification of triacylglycerols (sunflower oil) with methanol. Samples obtained with initial composition 2CaO center dot SiO2 and 3CaO center dot SiO2 calcined at 700 degrees C, and 3CaO center dot SiO2 calcined at 900 degrees C had high catalytic activity, resulting with triacylglycerols conversion and fatty acids methyl ester formation (FAME or biodiesel) above 96%. The activity of these samples can be attributed to the existence of free CaO defined by CaO/Ca2SiO4 complex mixture. The effect of different amount of catalyst used for transesterification (0.2-2 wt%) was analyzed using the most active catalyst i.e. 3CaO center dot SiO2 calcined at 700 degrees C as well as possibility of its reuse for biodiesel synthesis. It was also found that CaSiO3, Ca3Si2O7 and Ca2SiO4, phases did not possess catalytic activity. (C) 2019 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.