Several silicas (MCM-41, SBA-15 and HMS) were acid-modified by incorporating aluminium or by introducing phosphorus species or sulfonic groups. The modified silicas maintained mesostructural ordering and a narrow pore size distribution. However, Their surface area and pore volume was lower than that of unmodified samples. The incorporation of aluminum in the structure of MCM-41 and SBA-15 increased the amount of Bronsted acid sites, leading to greater catalytic activity (i.e., higher conversion values) for glycerol etherification with isobutene than pure silicas, but their relatively weak acid strength resulted in low selectivity to di- and tri-tertiary butyl ethers of glycerol (h-GTBE). The introduction of phosphoric groups, with higher acidity strength, improved the selectivity to h-GTBE, and glycerol triether was detected in low amounts. Interestingly, HMS synthesized with dodecylamine and later sulfonated exhibited total conversion and 84% of selectivity to h-GTBE (26% to glycerol triether) after 24 h of reaction. The presence of textural mesoporosity in HMS reduced diffusion limitations, and consequently increased the incorporation of sulfonic groups and their accessibility, leading to higher catalytic activity. (C) 2013 Elsevier B.V. All rights reserved.