In this study, two different types of hybrid porous organic polymers (POPs), polyhedral oligomeric silsesquioxane tetraphenylpyrazine (POSS-TPP) and tetraphenylethene (POSS-TPE), were successfully synthesized through the Friedel−Crafts polymerization of tetraphenylpyrazine (TPP) and tetraphenylethene (TPE), respectively, with octavinylsilsesquioxane (OVS) as node building blocks, in the presence of anhydrous FeCl₃ as a catalyst and 1,2-dichloroethane at 60 °C. Based on N₂ adsorption and thermogravimetric analyses, the resulting hybrid porous materials displayed high surface areas (270 m²/g for POSS-TPP and 741 m²/g for POSS-TPE) and outstanding thermal stabilities. Furthermore, as-prepared POSS-TPP exhibited a high carbon dioxide capacity (1.63 mmol/g at 298 K and 2.88 mmol/g at 273 K) with an excellent high adsorption capacity for iodine, reaching up to 363 mg/g, compared with the POSS-TPE (309 mg/g).