The partial exchange of tin with the protons of 12-tungstophosphoric acid (TPA) results in a highly active heterogeneous catalyst for benzylation of arenes with benzyl alcohol as benzylating agent. The catalysts were characterized by X-ray diffraction, Laser-Raman and FT-IR of pyridine adsorption. The catalytic activity depends significantly on the extent of tin exchanged with the protons of heteropoly tungstate. The characterization results suggest the presence of Lewis acidic sites by the exchange of tin. The catalyst with partial exchange of Sn showed high benzylation activity, which in turn related to variation in acidity of the catalysts. The catalyst is highly active for benzylation reaction irrespective of the nature of substituted arenes and benzyl alcohols. These catalysts are highly active compared to other acid catalysts used for benzylation of different arenes. The catalyst is easy to separate from reaction mixture and exhibit consistent activity upon reuse. The plausible reaction mechanism based on the role of both Lewis and Bronsted acid sites of the catalyst was discussed.