ZrO2-doped TiO2 hollow nanospheres with anatase phase are efficiently fabricated via functionalized negatively charged polystyrene (PS) spheres without any surfactant or polyelectrolyte. The resulting Ti1-xZrxO2 (hereafter denoted as TZ) hollow nanospheres are characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), powder X-ray diffraction (XRD), Laser Raman spectroscopy (LRS), X-ray photoelectron spectroscopy (XPS), X-ray fluorescence spectroscopy (XRF), nitrogen sorption, and UV-vis diffuse reflectance spectroscopy (UV-vis). The Zr4+ incorporation decreases the anatase crystallite size, increases the specific surface area, and changes the pore size distribution. Furthermore, it induces enrichment of electron charge density around Ti4+ ions and blueshift of absorption edges. The TZ hollow nanospheres doped with moderate ZrO2 (molar ratio, Ti:Zr = 10:1) exhibit better photocatalytic activity than the other samples for the degradation of rhodamine B in aqueous solution, which is correlated with the effect of Zr4+ doping on the physicochemical properties in terms of surface structures, phase structures, and the electronic structures. (C) 2011 Published by Elsevier Inc.