A systematic study was conducted to evaluate the effect of different transition metal oxide loaded on phosphated alumina as catalysts for the gas-phase dehydration of glycerol. The series of MeO-Al(2)O(3)-PO(4) catalysts at the constant Me:Al ratio was prepared by impregnation of alumina and characterized with respect to their textural properties, crystallinity, acidity and reducibility. Catalytic performance was tested at the constant operating conditions in the presence of steam. It was found that conversion, and acrolein formation increased with the increase of the total catalyst acidity: i.e., the selectivity to acrolein increased in the order: Ce < Mn < Cr < V similar to Fe < Cu < Mo < W. The highest selectivity towards acrolein (54%) was observed over W contained catalyst after a long-term test, i.e., 30 h. For Ce, Fe and Cr catalysts low selectivity to acrolein (12-23%) was observed. Contrary CuO(x)-Al(2)O(3)-PO(4) catalyst favored the formation of acetol (50%). In the case of Cr-, Mn- and V-containing alumina phosphates an enhanced formation of acetaldehyde and CO(x) was observed as a result of destructive glycerol cleavage. The V- and Fe-containing catalysts promote the formation of allyl alcohol. Finally, the change of the total acidity, oxidation state and crystallinity for spent catalysts was studied by NH(3)-TPD, TPO, TPR and XPS analysis. In general, MO-Al(2)O(3)-PO(4) catalysts showed improved stability against deactivation which can be attributed to the oxidative properties of the transition metal oxide components that enhance coke removal. (C) 2011 Elsevier B.V. All rights reserved.