In this work, the H3PW12O40 heteropolyacid, a versatile Bronsted acid catalyst promoted a selective conversion of glycerol into mono and diacetylglycerol, in reactions with acetic acid under mild conditions. The activity of the H3PW12O40 catalyst was compared to other Bronsted acid catalysts commonly used in esterification reactions (i.e. p-toluene sulfonic acid and sulfuric acid). The highest glycerol conversions were achieved in H3PW12O40-catalyzed esterification reactions. We demonstrated that unlikely than others homogeneous catalysts, H3PW12O40 may be repeatedly used without loss activity; this way it is also an attractive alternative that may avoid the serious drawbacks of the solid catalysts such as leaching and deactivation. Effects of the HOAc:glycerol molar ratio, acid strength and concentration of the catalysts were also assessed. Additionally, activation energy of the H3PW12O40-catalyzed esterification of glycerol was determined. (C) 2012 Elsevier B.V. All rights reserved.