A meso/macroporous interconnected polymer sorbent was prepared for CO2 capture by means of suspension polymerization of water-in-oil emulsion in aqueous solution. In the emulsion, poly(ethyleneimine) was dissolved in the water phase and enveloped into the oil phase containing glycidyl methacrylate and trimethylolpropane triacrylate. After polymerization and dehydration, poly(ethyleneimine) chains were grafted onto the macroporous surface of poly(glycidyl methacrylate-trimethylolpropane triacrylate) via the reaction between amine and epoxy groups. Physicochemical characterizations were carried out to evaluate its comprehensive performance in the adsorption/desorption process. The sorbent has exhibited optimum porous structure, high CO2/N-2 selectivity, acceptable CO2 uptake, and enhanced anti-oxidation and anti urea capacities. Notably, the energy penalty for sorbent regeneration is 2.31 MJ.kg(-1)(CO2), lower than the consumptions in the systems of alcohol amine absorption or poly(ethyleneimine)-silica adsorption.