Zirconium-supported Me(VI) oxide (Me = Cr, Mo, W) was prepared by the equilibrium adsorption method at pH values 2 and 8 by using as a support either hydrous [ZrO2(383)] or thermally pretreated zirconium oxide [ZrO2(T)]. The prepared solids were characterized by X-ray photoelectron spectroscopy, surface area determinations, electron scanning microscopy and analytical methods. Samples of definite grain size ranges of ZrO2(383) were also compared. The results show that the W-containing samples based on ZrO2(383) differed from Cr- and Mo-samples in the uptake dependence on pH. Despite its higher specific surface area, ZrO2(383) had a smaller W uptake than ZrO2(T). This behavior depends on the polyoxometalate anion size and the microporous structure of hydrous zirconium oxide. The depth of penetration of the Cr(VI), Mo(VI), and W(VI) anionic species in the grains of the ZrO2(383) support was estimated by quantitative XPS measurements and by electron microscopy determinations. The nuclearity of the adsorbed species is also briefly discussed.