The properties of nanosized sorbents prepared by high-energy milling from microcrystalline powder of titanium dioxide of rutile modification have been studied. It was established that milling to an average crystallite size of ~30 nm and ultraviolet illumination significantly improved the sorption properties of rutile with respect to chromium compared with those of the starting material and the ability of Cr(VI) to be reduced to Cr(III) in its presence. The maximum removal of Cr(VI) from aqueous solutions with a concentration of 50 mg/L was achieved under UV illumination in an acetate buffer medium at pH 4–5 and a content of ground rutile of 16.7 g/L. A mechanism of adsorption was proposed.