Extended porous silica films with thicknesses in the range of 60 to 130 mum and pores on both the meso- and macroscale have been prepared by simultaneously using porous membrane templates and amphiphilic supramolecular aggregates as porogens. The macropore size is determined by the cellulose acetate or polyamide membrane structure and the mesopores by the chosen ethylene-oxide-based molecular self-assembly (block copolymer or non-ionic surfactants). Both the template and the porogen are removed during an annealing step leaving the amorphous silica material with a porous structure that results from sot-gel chemistry occurring in the aqueous domains of the amphiphilic liquid-crystalline phases and casting of the initial template membrane. The surface area and total pore volume of the inorganic films vary from 473 to 856 m(2) g(-1), and 0.50 to 0.73 cm(3) g(-1), respectively, depending on the choice of template and porogen. The combined benefits of both macro- and mesopores can potentially be obtained in one film. Such materials are envisaged to have applications in areas of large molecule (biomolecule) separation and catalysis. Enhanced gas and liquid flow rates through such membranes, due to the presence of the larger pores, also makes them attractive as supports for other catalytic materials.