A continuing challenge for materials chemists and engineers is the ability to create multifunctional composite structures with well-defined superimposed structural order from nanometer to micrometer length scales. Materials with three-dimensional structures ordered over multiple length scales can be prepared by carrying out colloidal crystallization and inorganic/organic cooperative self-assembly within microchannel networks. The resulting materials show hierarchical ordering over several discrete and tunable length scales ranging from several nanometers to micrometers. These patterned porous materials hold promise for use as advanced catalysts, sensors, low-k dielectrics, optoelectronic and integrated photonic crystal devices.