An solar-light-driven and bifunctional photocatalyst was designed for photo-reduction of Cr(VI) and selective photo-oxidation of benzyl alcohol into benzaldehyde in the presence of water under ambient conditions. Double-shelled and sandwiched TiO2@Pt@CeO2 hollow spheres were prepared by using functionalized polystyrene spheres, sol-gel, hydrothermal reaction, and calcination. The Pt nanoparticles (NPs) were controllably loaded between the TiO2\\\ shell and CeO2 shell. Under solar light irradiation, the photo-reduction rate of Cr(VI) (mu molh(-1)) was in the order of TiO2@Pt@CeO2 (1.901)>TiO2@CeO2 (1.424)>TiO2 (1.040)> CeO2 (0.992). Among the above-mentioned photocatalysts, the conversion rate of benzyl alcohol for TiO2@Pt@CeO2 was also the best. These results were attributed to the combination of TiO2 and CeO2 as photocatalyst and oxygen buffer, the double-shelled and sandwiched nanostructure, and the addition of Pt NPs as cocatalyst and electron trap site, which could store and shuttle photo-generated electrons, reduce the recombination of the electron-hole, and then enhance photo-generation of active radicals. This conclusion was verified by the electron paramagnetic resonance (EPR) spectroscopy. Considering the versatile combination of photocatalyst, oxygen buffer and cocatalyst, this work could provide new insights into the design of high-performance bifunctional photocatalysts for heavy metal removal and selective synthesis. (C) 2017 Elsevier B.V. All rights reserved.