Heck coupling reactions are introduced as an efficient method to prepare porous polymers. Novel inorganic-organic hybrid porous polymers (HPPs) were constructed via Heck coupling reactions from cubic functional polyhedral oligomeric silsesquioxanes (POSS), iodinated octaphenylsilsesquioxanes (OPS) and octavinylsilsesquioxanes (OVS) using Pd(OAc)2/PPh3 as the catalyst. Here, two iodinated OPS were used, IOPS and p-I8OPS. IOPS was a mixture with 90% octasubstituted OPS (I8) and some nonasubstituted OPS (I9), while p-I8OPS was a nearly pure compound with 99% I8 and 93% para-substitution. IOPS and p-I8OPS reacted with OVS to produce the porous materials HPP-1 and HPP-2, which exhibited comparable specific surface areas with SBET of 418 +/- 20 m2 g1 and 382 +/- 20 m2 g1, respectively, with total pore volumes of 0.28 +/- 0.01 cm3 g1 and 0.23 +/- 0.01 cm3 g1, respectively. HPP-1 showed a broader pore size distribution and possessed a more significant contribution from the mesopores, when compared with HPP-2, thereby indicating that IOPS may induce more disorder because of the geometrical asymmetry. HPP-1 and HPP-2 possessed moderate carbon dioxide uptakes of 134 and 124 cm3 g1 at 1 bar at 195 K, making them promising candidates for CO2 capture and storage. The synthesized porous polymers may be easily post-functionalized using the retained ethenylene groups.