Hypercrosslinked polystyrene (HCLPS) microspheres with ultrahigh surface area have been prepared via dispersion polymerization and post cross-linking. The microspheres were predominantly microporous and exhibited surface area of 1161 m(2)/g, and the total pore volume of 0.72 cm(3)/g. HCLPS microspheres could be enough swollen in organic solvent and water in spite of thermodynamic compatibility. Furthermore, gas storage capacity of HCLPS microspheres was also investigated, and the results indicated that the microspheres could reversibly store up to 2.27 wt% H-2 at lbar/77.3 K, and 14.8 wt% CO2 at lbar/273 K. Therefore, as-prepared HCLPS microspheres were promising materials for use in packing materials of HPLC, adsorbents for organic compound, and gas storage materials. (C) 2017 Elsevier B.V. All rights reserved.