Methods of polystyrene beads producing with properties appropriate for catalyst and adsorbent synthesis have been investigated. Hierarchical silicalite-1 and Fe-silicalite-1 with zeolitic MFI structure, as well as three-dimensionally ordered titania, silica, alumina and zirconia have been prepared by hard-templating method using polystyrene beads. The materials were characterized by X-ray diffraction, scanning and transmission electron microscopies, low-temperature nitrogen adsorption technique and mercury porosimetry. Developed meso- and macroporous structure of the templated materials facilitated the supply of macromolecular reactants to the material surface and reduced the negative effect of byproduct deposition, resulting in favored advantages of the materials in a wide range of processes: hydroconversion of heavy oil, wet hydrogen peroxide oxidation of organic substrates in water, photocatalysis and gas chromatographic analysis. The obtained results of the material applications showed their potential attractiveness as catalysts and adsorbents.