Films with polymodal porosity (macro-, meso- and micropores) as well as complex materials compositions (different metals, different organic groups) were prepared. First, self-assembled polystyrene spheres on glass slides were coated with a sol prepared from tetraethoxysilane, phenyl- or methyltriethoxysilane and ethyl acetoacetate-stabilized zirconium propoxide or titanium iso-propoxide in the presence of a non-ionic surfactant. Macropores were created by dissolving the polystyrene porogen. Subsequent calcination at different temperatures resulted in the sequential formation of meso- and micropores. Post-calcination treatment with phosphonic acids allowed the introduction of a second type of organic group.