The synthesis of highly ordered macroporous materials has been accomplished in a straightforward, single-step reaction. Inorganic frameworks composed of oxides of Si, Ti, Zr, Al, W, Fe, Sb, and a Zr/Y mixture were formed from metal alkoxide precursors templated around polystyrene (latex) spheres. Monodisperse latex spheres were ordered into closepacked arrays by centrifugation. The interstices between latex spheres were permeated by the alkoxide, which hydrolyzed and condensed. An inorganic framework was formed upon drying. Removal of the latex spheres was accomplished by either calcination at temperatures between 450 and 1000 °C or extraction with a tetrahydrofuran/acetone mixture. The resulting products consisted of periodic, interconnected networks of monodisperse submicron pores extending over hundreds of micrometers. Depending on the technique of template removal, various phases of the inorganic oxide could be formed. For example, in the case of titania, an amorphous phase was formed upon extraction of TiO2 and anatase by calcination at 450 °C. The synthesis has also been expanded to other compositions including aluminophosphates and hybrid organosilicates, as well as silicates with bimodal distributions of meso- and macropores. The materials presented in this paper show the diversity of macroporous materials achievable with this technique. These structures could potentially find applications as Chromatographie support materials, solid catalysts, battery materials, thermal insulators, or photonic crystals.