Etherification of glycerol by isobutylene was conducted in a batch mode using acidic and partially neutralized Amberlyst-15 ionic resin p-toluenesulfonic acid silicotungstic acid cesium salt of silicotungstic acid and ionic liquid containing sulfonic acid groups All the catalysts are comparable in terms of the initial rate of glycerol conversion into mono-ether (except cesium salt of heteropolyacid) but differ substantially with respect to the yields of higher ethers of glycerol Ionic liquid and heteropolyaad are immiscible/insoluble in higher ethers of glycerol As a result they have unique capability of suppressing the formation of tri-ether during the initial stage of glycerol conversion Acidic Amberlyst-15 in the form of fine powder has the highest activity per unit weight for glycerol etherification and relatively high activity in isobutene oligomerization Partial exchange of acidic protons with cations Na+ Ag+ Mg2+ and Al3+ decreases the rates of all the processes but isobutylene oligomenzation is suppressed more efficiently Ag+- and Al3+-modified Amberlyst demonstrates higher yields of tri-ether and has specific pattern of interaction with gaseous isobutene distinctive to other metal-substituted Amberlysts (C) 2010 Elsevier B V All rights reserved