A series of hybrid nanoporous polystyrenes were synthesized from commercial polystyrene (PS) and cubic octavinylsilsesquioxane (OVS) via the Friedel-Crafts reaction. The porosity of the resulting hybrid polymers could be fine-tuned by varying the ratio of PS and OVS. The resulting polymers, HCP-1 to HCP-9 had apparent Brunauer-Emmett-Teller surface areas (S BET ) in a range of 2.6 to 767 m 2 g À1 , with total pore volumes in the range of 0.36 to 0.90 cm 3 g À1 . The S BET was maximum when OVS loading was 9.1 wt%; it then decreased to almost no porosity before increasing again with the increase of OVS loading. The thermal decomposition temperatures of the hybrid polymers were close to pure PS under a N 2 atmosphere, but the residues increased with the increase of OVS loading. The gas sorption applications revealed that HCP-3 possessed H 2 uptake of 3.01 mmol g À1 (0.60 wt%) at 77 K and 1.01 bar and CO 2 uptake of 1.12 mmol g À1 (4.93 wt%) at 298 K and 1.01 bar. † We dedicate this paper to Prof. Hongzhi Liu's mother, who is dearly missed by all members of the family.‡ Electronic supplementary information (ESI) available: The elemental analysis results of HCP-1 to HCP-9; FT-IR spectra of HCP-1, HCP-2, HCP-5 to HCP-7; FE-SEM images of HCP-3 to HCP-9 with different magnications and areas. See