Ternary Cu/TiO2/rGO photocatalysts with varying Cu and graphene loadings were prepared by a solvothermal method. Pure anatase TiO2 hollow spheres (THS) were prepared with titanium butoxide, ethanol, ammonium sulphate, and urea via a hydrothermal method; Cu nanoparticles were subsequently loaded on the surface of the hollow spheres by wet impregnation. During the solvothermal process, deposition and well dispersion of Cu-TiO2 hollow spheres composites onto graphene oxide surface, as well as the reduction of graphene oxide to graphene were achieved. The morphological and structural properties of the prepared samples were characterized by Brunauer-Emmett-Tellet (BET), X-ray Diffraction (XRD), Scanning Electron Microscope (SEM), UV-vis DRS, and Photoluminescence (PL). The activity of the prepared catalyst was tested for hydrogen production via simultaneous photocatalytic water-splitting and glycerol reforming under natural solar light irradiation. The excellent photocatalytic activity of the ternary Cu/THS/graphene catalyst is attributed to the graphene sheets, which acts as both storage and transferor of electrons generated at the Cu and TiO2 heterojunction, thus increasing the electron-hole pair separation. (C) 2020 Published by Elsevier Ltd.