12-Tungstophosphoric acid (TPA) was modified systematically by incorporating niobium into its primary and secondary structure. TPA supported on niobia catalyst was also prepared by impregnation method. These catalysts were characterized by FT-infra red, X-ray diffraction, Laser Raman, X-ray photo electron spectroscopy, X-ray absorption spectroscopy, UV-vis diffuse reflectance spectroscopy, solid state (31)p nuclear magnetic resonance spectroscopy, temperature programmed desorption of ammonia and pyridine adsorbed FT-IR spectroscopy. Characterization results suggest the presence of intact Keggin structure after modification of parent TPA. Incorporation of Nb into the secondary structure results in generation of Lewis acidic sites. Nb containing TPA catalysts exhibited high acidity compared to the TPA supported on niobia catalyst. The activity of the catalysts was evaluated for benzylation of anisole with benzyl alcohol. Catalyst activity depended on the location of niobium ion in the heteropoly tungstate. (C) 2015 Elsevier B.V. All rights reserved.