Different types of porous materials have been developed for the efficient separation of CO2 from mixtures of gases. Nevertheless, the most porous materials cannot be used for extensive industrial applications due to their non-negligible disadvantages, such as complex synthesis routes, expensive monomers, and/or costly catalysts. Therefore, a strategy for fabricating a series of polyhedral oligomeric silsesquioxane (POSS)-based porous organic polymer materials (PBPOPs) was developed through the simple condensation reaction of octaphenylsilsesquioxane and different bromine-containing monomers. It was found that PBPOP-2 exhibits the best CO2 adsorption amount of 41 cm3·g−1 at 273 K and 760 mmHg based on the accessible specific surface area, large pore volumes, and accessible pore sizes. Furthermore, PBPOP-2 exhibits efficient CO2/N2 selectivity and complete regeneration under mild conditions, which demonstrates the potential for the selective separation of CO2 from gas mixtures. This work provides a new route to developing POSS-based POPs for CO2-capture applications.