The aim of the present study was to synthesize a photocatalyst on the basis of TiO2 with kaolin as the support material. Properties such as layered structure and a suitable particle size of kaolin could be beneficial in the production of a high-quality and relatively cheap photocatalyst on an industrial scale. Homogeneous hydrolysis with urea as a precipitation agent and kaolin as support material was used to obtain a kaolin surface covered with TiO2. Samples were characterized by means of X-ray powder diffraction, infrared and Raman spectroscopy, high-resolution transmission electron microscopy, Brunauer-Emmett-Teller surface area, and Barrett-Joyner-Halenda porosity determination. Photocatalytic activity was assessed by a Reactive Black 5 azo dye discoloration in a water suspension and by acetone decomposition on a thin layer of sample in a gas phase. The characterization confirmed that the well crystallized TiO2 was distributed effectively over the whole surface of a kaolin substrate, and photocatalytic tests revealed that the active surface layer of titania particles on kaolin performed well, suggesting that kaolin acts as a suitable support.