Using (C 16 H 36 O 4 )Ti, Gd 2 O 3 and HNO 3 as raw materials, TiO 2 and TiO 2 :Gd 3? hollow spheres with different Gd dopant concentrations of 0.25, 0.5, 1, 1.5 and 2 mol% were obtained with the assistance of the carbon sphere templates. The morphology, structure, specific surface area and photocatalytic properties of the prepared hollow spheres were studied by scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller and UV-Vis 2550 spectrophotometer, respectively. Several factors influencing the photocatalytic activities of the samples were studied, which include pH value of the solutions, Gd dopant concentrations, amount of the additive catalysts and types of the dyes. Graphical Abstract In this work, fabrication of TiO 2 : Gd 3? hollow spheres (b) was obtained with the assistance of the carbon sphere template (a). Characterization of the samples was also reported in this paper.