Mesoporous powders of transition-metal oxides, TiO2, ZrO2, HfO2, Nb2O5, and Ta2O5, pure from organic impurities were produced by a rapid single-step thermohydrolytic approach. The obtained materials display an impressively large active surface area and sharp pore-size distribution, being composed of partially coalesced uniform nanoparticles with crystalline cores and amorphous shells. They reveal extremely high adsorption capacity in removal of CrVI anions from solutions (25.8 for TiO2, 73.0 for ZrO2, and 74.7 mg g−1 for Nb2O5 in relation to the Cr2O72− anion), making them very attractive as adsorbents in water remediation applications. The difference in adsorption capacities for the studied oxides may be explained by variation in surface hydration and surface-charge distribution.