Two novel thiophene-based conjugated networks CMPs-TIT and CMPs-DTBT were designed and prepared with different steric configuration building blocks by FeCl3 oxidative coupling polymerization. UV-vis spectra, FE-SEM and TEM images showed CMPs-TTT and CMPs-DTBT having the different aggregated morphologies. After porous analysis and gas adsorption test, the result showed CO2 uptake capacity of CMPs-DTBT with amorphous aggregation model is 2.88 times and 2.66 times greater than that of CMPs-TTT with large lamellar structure model at 273 K and 298 K (1.0 bar), respectively. As a result, this communication proved that change the topological structure of the polymer can influence the CO2 adsorption capacity significantly. (C) 2014 Elsevier Inc. All rights reserved.