The hierarchical Ag/AgCl-TiO2 hollow spheres were synthesized by depositing Ag/AgCl nanoparticles on TiO2 hollow spheres via a precipitation photoreduction method, and they were further characterized using TGA, SEM, TEM, XRD, XPS, UV-vis DRS and photoelectric chemical analysis. The analysis showed that the hierarchical Ag/AgCl-TiO2 hollow spheres exhibited the highest photocatalytic activity, which was approximately 13 times higher than that of TiO2 hollow spheres. The high photocatalytic activity of the composites is due to efficient electron-hole pairs separation at the photocatalyst interfaces, and localized surface plasmon resonance of Ag nanoparticles formed on AgCl particles in the degradation reaction. (C) 2016 Published by Elsevier B.V.