Aluminium exchanged heteropoly tungstate (AITPA) supported on titania catalysts were prepared and characterized by FT-Infra red, X-ray diffraction, Laser Raman, temperature programmed desorption of ammonia and X-ray photo electron spectroscopy. The catalytic properties of the catalysts were evaluated for benzylation of anisole with benzyl alcohol. The catalysts showed high activity for anisole benzylation and the catalyst with 20 wt% of AITPA exhibited highest activity. The presence of AI resulted in generation of Lewis acidic sites. Acidic property and chemical structure of AITPA on different supports also evaluated by supporting AITPA on Nb(2)O(5), ZrO(2) and SnO(2). The catalytic activity of these catalysts is in the order of AITPA/TiO(2) > AITPA/SnO(2) > AITPA/ZrO(2) > AITPA/Nb(2)O(5). The benzylation activity and selectivity towards benzylated product also depends on the reaction temperature, catalyst weight and anisole to benzyl alcohol ratio. (C) 2011 Elsevier B.V. All rights reserved.