Two different schemes were adopted to fabricate ordered macroporous structures with face centered cubic lattice of air spheres. Monodisperse polymeric latex suspension, which was synthesized by emulsifier-free emulsion polymerization, was mixed with metal oxide ceramic nanoparticles, followed by evaporation-induced self-assembly of the mixed hetero-colloidal particles. After calcination, inverse opal was generated during burning out the organic nanospheres. Inverse opals made of silica or iron oxide were fabricated according to this procedure. Other approach, which utilizes ceramic precursors instead of nanoparticles was adopted successfully to prepare ordered macroporous structure of titania with skeleton structures as well as lithium niobate inverted structures. Similarly, two different schemes were utilized to obtain disordered macroporous structures with random arrays of macropores. Disordered macroporous structure made of indium tin oxide (ITO) was obtained by fabricating colloidal glass of polystyrene microspheres with low monodispersity and subsequent infiltration of the ITO nanoparticles followed by heat treatment at high temperature for burning out the organic microspheres. Similar random structure of titania was also fabricated by mixing polystyrene building block particles with titania nanoparticles having large particle size followed by the calcinations of the samples.