The kaolinite/TiO 2 composite was prepared using thermal hydrolysis of kaolinite/titanyl sulphate suspension and characterized by XRFS, XRPD, SEM and N 2 physical adsorption. Its photocatalytic properties were evaluated by photocatalytic reduction of CO 2 by water and compared with commercial TiO 2 photocatalyst Degussa P25. Results showed that the yields of CO 2 photocatalytic reduction products methane and methanol were higher over a kaolinite/TiO 2 composite than over commercial TiO 2 (Degussa P25) in spite of smaller proportion of TiO 2 in the composite. Introducing of TiO 2 nanoparticles into the kaolinite structure caused a decrease of anatase crystallite size. Kaolinite can also change acidobasic properties of catalyst surface, inhibit the recombination of electron–hole pairs and prevent the formation of TiO 2 aggregates in suspension. These facts can contribute to the observed higher photocatalytic efficiency of kaolinite/TiO 2 compared to the commercial TiO 2 photocatalyst.