In recent years, heterogeneous photocatalysis has gained enormous interest due to increasing concerns about environmental pollution. Here we propose a facile approach to synthesize cauliflower-like CeO 2 -TiO 2 hybrid structures by magnetron reactive sputtering, exhibiting an extremely high photocatalytic activity. While heating and air-quenching of the sputter deposited TiO 2 thin film (first layer) triggered the formation of a nanocrack network, the second heat-treatment led to transformation of the CeO 2 film (second layer) into CeO 2 nanoclusters (NCs). We attribute the resulting high photocatalytic activity to the confined structure of the CeO 2 NCs and the CeO 2 -TiO 2 interface, which allows Ce 3+ /Ce 4+ dynamic shifting. In addition to high photocatalytic activity in an aqueous medium, the prepared CeO 2 -TiO 2 hybrid structures exhibited significant self-cleaning properties in air (non-aqueous).