Ordered porous materials were produced from macrocrystalline emulsion templates. The templates were prepared by a repeated fractionation technique from polydisperse aqueous and nonaqueous emulsions with a drying control chemical additive. The aqueous emulsion drops tended to migrate and flee in relatively mobile local regions during the capturing process,which eventually led to the nonuniform pore distribution in the final inorganic matrix. On the other hand, the monodisperse nonaqueous emulsions led to uniformly distributed pore structure.