Glycerol is currently produced in waste quantities as a byproduct from the production of biodiesel. It is normally generated at the rate of 1 mol of glycerol for every 3 mol of methyl esters synthesized; approximately 10 wt% of total product. Therefore, to make the biodiesel sector sustainable and more profitable all of the produced glycerol should be efficiently processed. Promising route for glycerol valorization is its catalytic dehydration to acetol and/or acrolein. In this work acid-base properties of zirconia based, titania based and calcium phosphate catalysts were fully characterized by adsorption calorimetry and FTIR spectroscopy of appropriate probe molecules. Catalytic behavior of studied materials was tested in the gas phase dehydration of glycerol. Special attention is given to the correlation between catalytic activity and surface acid–base properties, which are essential to the mechanism of the reaction.