The heterogeneous catalytic etherification of glycerol with tert-butyl alcohol was investigated in presence of lab-made silica supported acid catalysts. As reference, two commercial acid ion-exchange resins were also used. Experiments were carried out in batch mode at T-R ranging from 303 to 363 K. An increase in reaction temperature favors the formation of di-substituted ethers. The etherification reaction proceeds according to a consecutive path and the surface reaction between adsorbed glycerol and protonated tert-butanol (tertiary carbocation) can be considered as the rate determining step. Steric hindrance phenomena and water hinder the formation of tri-substituted ether (TBGE). As expected, water removal was necessary to allow the higher ethers formation. The specific activity (turnover frequency, TOF) of A-15 catalyst is significantly higher than that of the other studied acid systems, due to the wide pore diameter that allows an easier accessibility of the reagent molecules. (C) 2009 Elsevier B.V. All rights reserved.