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Potassium and cesium salts of tungstophosphoric acid were prepared by precipitation method. For sake of comparison HPW, potassium and cesium tungstophosphates were supported on silica (20 wt%) by wet impregnation method. The catalysts were characterized by XRD, nitrogen adsorption-desorption measurements at 77 K, and the catalytic activity has been studied by using the catalytic conversion of tert-butanol at temperatures between 323 and 423 K. The results revealed that all of the catalysts were active and selective towards dehydration of tert-butanol yielding isobutene with low amount of isooctene as result of oligomerization process. Substitution of one proton of HPW by cesium or potassium cation exerted no measurable effect on the catalytic activity. The conversion over unsupported catalysts increased by increasing the cation content per Keggin unit of x ≥ 2. Supporting the previous salts on SiO2 resulted in a significant decrease in the catalytic activity upon increasing cation content. Activation energy was calculated for different solids.