a b s t r a c tThree carbazole based building blocks with similar propeller-like steric configuration are designed and synthesized. The polycarbazole networks P-4, 4 0 -biscarbazolyl-phenyl (P-BCz), P-tetracarbazolyl-pdifluorobenzene (P-TCz) and P-hexacarbazolyl-phenyl (P-HCz) are obtained with high surface areas and uniform ultramicropores. The aggregation morphologies of networks vary from regular spherical particles, ribbon-like structure to large lamellar structure as the number of carbazole increased around the benzene ring. The networks P-TCz, with four carbazole decorating on the benzene ring, have the largest surface area and highest gas uptake ability among the three networks. However, the CO 2 and CH 4 isosteric enthalpies increased linearly with increasing the number of carbazole. The networks P-HCz with six carbazole show the excellent CO 2 /N 2 separative capacity (107 at 273 K, and 127 at 298 K), which is among the highest reported about CO 2 separation using organic pore networks. Fine designing and tailoring the topological structure of monomer can control the adsorption properties and optimize the gas uptake performance.