Hollow spheric Ag-Ag2S was prepared by in-situ chemical transforming of sacrificial Cu2S templates with AgNO3 solution. Hollow spheric Ag-Ag2S/TiO2 composites were then prepared by assembling TiO2 grains around the Ag-Ag2S spheres with hydrothermal treatment of Ag-Ag2S with Ti precursor at 180 degrees C. X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM), Inductively coupled plasma-atomic emission spectroscopy (ICP-AES) were adopted to characterize the as-prepared composite. Ag-Ag2S/TiO2 composite has obvious absorption at both UV and visible regions, and shows prior photocatalytic activity for the reduction of Cr(VI) under both UV and visible irradiation. Particularly, the Ag-Ag2S/TiO2-5 and Ag-Ag2S/TiO2-10 show the highest activity for the photocatalytic reduction of Cr(VI) under UV and visible irradiation, respectively. The Schotty barrier between Ag and Ag2S (and TiO2 as well) and the heterojunction between the Ag2S and TiO2 are suggested as the main reasons that enhance the photocatalytic reduction of Cr(VI). The photocatalytic activity of Ag-Ag2S/TiO2 composite is maintained well after being recycled several times. (C) 2015 Elsevier B.V. All rights reserved.