A novel approach to prepare double-shelled, nanostructured hollow spheres with positively and negatively charged was proposed. If the difference in isoelectric points between MxO and NyO was large enough, at a certain pH range, the inner and outer shell of double-shelled MxO@NyO hollow spheres were positively and negatively charged, respectively. A proof-of-concept was shown, using WO3 and TiO2 as anionic and cationic building subunits, respectively. The nanoparticles of WO3 and TiO2 were coated successively onto the functionalized polystyrene (PS) template beads, the resulted PS@WO3@TiO2 nanocomposites were calcined at elevated temperature, and then double-shelled WO3@TiO2 hollow spheres were obtained. The dispersity, morphology, size, and lattice of these hollow spheres were tested by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The presence and purity of both WO3 and TiO2 phases were confirmed by electron energy loss mapping analysis and X-ray diffraction analysis (XRD). The specific surface area and the average pore diameter of these hollow spheres were 53.04 m(2)/g and 8.042 nm, respectively. The photocatalytic activity for the degradation of cationic and anionic aromatic pollutants was in the order of double-shell hollow spheres WO3@TiO2 > single-shell WO3-TiO2 > P25, i.e., the synergistic effect of coupling TiO2 with WO3 on photocatalytic performance was proved by us. (C) 2014 Elsevier BM. All rights reserved.