The design and synthesis of new multifunctional organic porous polymers has attracted significant attention over the years due to their favorable properties, which make them suitable for carbon dioxide storage. In this study, 2-, 3-, and 4-hydroxybenzaldehyde reacted with phenyltrichlorosilane in the presence of a base, affording the corresponding organosilicons 1−3, which further reacted with benzidine in the presence of glacial acetic acid, yielding the organic polymers 4−6. The synthesized polymers exhibited microporous structures with a surface area of 8.174−18.012 m2 g−1, while their pore volume and total average pore diameter ranged from 0.015−0.035 cm3 g−1 and 1.947−1.952 nm, respectively. In addition, among the synthesized organic polymers, the one with the meta-arrangement structure 5 showed the highest carbon dioxide adsorption capacity at 323 K and 40 bar due to its relatively high surface area and pore volume.