Highly uniform 3-D ordered macroporous spheres in regular arrays were produced by a double templating process. The first template of larger silica balls produced the polymer skeleton for guiding the shape and size of the self-assembled superstructure of smaller polymeric balls, which are introduced subsequently into the internal space of the skeleton. The second templating with inorganic precursors has created novel superstructured materials, which could open up significant opportunities in a variety of areas ranging from absorbents/catalysts to novel photonic crystals.