A series of active and selective MCM-41 supported catalysts have been successfully prepared and used for bio-derived glycerol esterification with acetic acid to produce fuel additives. In the synthesis of MCM-41, an acidic hydrothermal synthesis route was used, and silicotungstic acid (STA) and zirconia (ZrO2) were added to the catalyst structure by wet impregnation. X-ray diffraction, nitrogen adsorption-desorption methods, scanning electron microscopy with energy-dispersive spectroscopy, and inductively coupled plasma-mass spectrometry analysis were used for characterizations of the catalysts. Diffuse reflectance infrared Fourier transform spectroscopy analyses of pyridine-adsorbed catalysts owns Lewis and Bronsted acidity hosting in one, which promotes the esterification reaction of glycerol into glycerol esters with high selectivity. Esterification of glycerol reactions were performed at temperature intervals of 105 degrees C-200 degrees C, with an amount of catalyst equal to 0.5 g, and glycerol/acetic acid molar ratio of 1:6 in a stirred autoclave reactor operated batchwise. STA and ZrO2-impregnated MCM-41 catalysts showed better performance with a complete glycerol conversion and high selectivity to triacetin.