The present study is focused on the etherification of biodiesel-derived glycerol with anhydrous ethanol over arenesulfonic acid-functionalized mesostructured silicas to produce ethyl ethers of glycerol that can be used as gasoline or diesel fuel biocomponents. Within the studied range, the best conditions to maximize glycerol conversion and yield towards ethyl-glycerols are: T = 200 degrees C, ethanol/glycerol molar ratio = 15/1, and catalyst loading = 19 wt%. Under these reaction conditions, 74% glycerol conversion and 42% yield to ethyl ethers have been achieved after 4 h of reaction but with a significant presence of glycerol by-products. In contrast, lower reaction temperatures (T = 160 degrees C) and moderate catalyst loading (14 wt%) in presence of a high ethanol concentration (ethanol/glycerol molar ratio = 15/1) are necessary to avoid the formation of glycerol by-products and maximize ethyl-glycerols selectivity. Interestingly, a close catalytic performance to that achieved using high purity glycerol has been obtained with low-grade water-containing glycerol. (C) 2011 Elsevier Ltd. All rights reserved.