Triple zirconia/boehmite/polymethyl acrylic acid layer-coated pigmentary rutile TiO2 nanocomposites were prepared by successive hydrolysis of zirconium sulfate and sodium meta-aluminate and in situ polymerization of methyl acrylic acid in aqueous solutions. Uniform, compact, and islandlike hydrous zirconia layers could be controllably coated on rutile TiO2 particles by adjusting the hydrolysis pH value. At a 1 wt % alumina loading, boehmite nanoparticles were deposited on the zirconia-coating layer to form an islandlike boehmite-coating layer, whereas at a 2 wt % alumina loading, in addition to the islandlike boehmite coating layer, a flocculent boehmite layer was deposited. The zirconia and boehmite layers anchored at their substrates through Zr-O-Ti and Al-O-Zr bonding, respectively. The zirconia-coating layer obviously improved the whiteness and brightness of the pigmentary rutile TiO2 powder. The binary zirconia/boehmite layers completely suppressed the photocatalytic activity of the rutile TiO2 powder under UV light irradiation. The boehmite layers with a large amount of OH groups caused the aggregation of TiO2@ZrO2@AlOOH nanocomposites. Anchoring polymethyl acrylic acid molecules at the TiO2@ZrO2@AlOOH nanocomposite improved its dispersion stability in water. The as-prepared TiO2@ZrO2@AlOOH@MAA nanocomposite (where MAA is polymethyl acrylic acid) can be used as a white pigment in water-based-coating materials.