Taking benefit of previously obtained results, stable complex organic–inorganic hybrid suspensions are successfully prepared by mixing a polystyrene latex aqueous suspension, a titania hydrosol and a nonionic triblock copolymer. These suspensions can be then deposited as thin films on dense or porous substrates. Solvent evaporation induces the formation of spherical micelles by self-assembly of the amphiphilic molecules during the drying of the films. Two types of isolated spherical macropores (few ten nanometers) and mesopores (4–5 nm) are generated inside the layers by the thermal removal of the polystyrene particles and of the micelles, respectively. The remaining inorganic network exhibits an additional interconnected microporosity with a mean pore size of 1.5 nm, resulting from the aggregation of the anatase nanoparticles. A complete removal of the templating units at low temperature is possible using the photocatalytic properties of the anatase network. Such layers exhibit attractive properties for the design of ceramic membranes. They can be advantageously used in order to increase the permeability of the separative layer and to reduce the number of intermediate layers of these asymmetric structures.