Ordered macroporous films of nanocrystalline TiN and amorphous SiNx on silica substrates have been prepared. This involved infiltration of sacrificial templates of close-packed polystyrene microsphere arrays with precursor materials, followed by pyrolysis under ammonia to remove the template and form the ceramic materials. TiN was prepared from a sol−gel route, whereas SiNx was introduced using a Si(NHMe)4 precursor solution. Hexane was found to be the solvent most compatible with the divinylbenzene-cross-linked polystyrene template and was used for both materials.