An effect of using different TiO2 polymorphs as support for H3PW12O40 heteropolyacid on the (photo)catalytic performance of the H3PW12O40/TiO2 catalyst was investigated. Two kinds of synthesis methods of the catalysts have been applied. In the first, the H3PW12O40/TiO2 catalyst was prepared by impregnation of either the pure anatase (A), or rutile (R), or a mixture of the two (P25) in a solution of H3PW12O40. In the second method, an additional pre-treatment is being applied to all three types of support, A, R and P25, consisting of hydrothermal sonication with KOH solution. The catalysts and supports were characterized by XRD, SEM, BET analysis and FTIR spectroscopy. Catalytic tests show that H3PW12O40/P25 catalyst exhibits a higher (photo)activity to n-butanol dehydration in gas phase compared to the catalysts supported on either of pure polymorphs and that the sonication pre-treatment did not improve the activity of the catalysts so prepared. The application of the not treated P25-the mixture of anatase and rutile as the support of heteropolyacid allowed to find the efficient heterogeneous catalyst.