Carbon dioxide emitted from existing coal-fired power plants is a major environmental concern due to possible links to global climate change. In this study, we expand upon previous work focused on aminosilane-functionalized polymeric hollow-fiber sorbents by introducing a new class of polyethyleneimine (PEI)-functionalized polymeric hollow-fiber sorbents for post-combustion carbon dioxide capture. Different molecular weight PEIs (Mn≈600, 1800, 10 000, and 60 000) were studied as functional groups on polyamide imide (PAI, Torlon) hollow fibers. This imide ring-opening modification introduces two amide functional groups and was confirmed by FTIR attenuated total reflectance spectroscopy. The carbon dioxide equilibrium sorption capacities of PEI-functionalized Torlon materials were characterized by using both pressure decay and gravimetric sorption methods. For equivalent PEI concentrations, PAI functionalized with lower molecular weight PEI exhibited higher carbon dioxide capacities. The effect of water in the ring-opening reaction was also studied. Up to a critical value, water in the reaction mixture enhanced the degree of functionalization of PEI to Torlon and resulted in higher carbon dioxide uptake within the functionalized material. Above the critical value, roughly 15 % w/w water, the fiber morphology was lost and the fiber was soluble in the solvent. PEI-functionalized (Mn≈600) PAI under optimal reaction conditions was observed to have the highest CO2 uptake: 4.9 g CO2 per 100 g of polymer (1.1 mmol g-1) at 0.1 bar and 35°C with dry 10 % CO2/90 % N2 feed for thermogravimetric analysis. By using water-saturated feeds (10 % CO2/90 % N2 dry basis), CO2 sorption was observed to increase to 6.0 g CO2 per 100 g of sorbent (1.4 mmol g-1). This material also demonstrated stability in cyclic adsorption-desorption operations, even under wet conditions at which some highly effective sorbents tend to lose performance. Thus, PEI-functionalized PAI fibers can be considered as promising material for post-combustion CO2 capture. Sucked in! Polyethyleneimine (PEI)-functionalized polymeric hollow-fiber sorbents for post-combustion carbon dioxide capture are described. Different molecular weight PEIs are studied as functional groups on polyamide imide (PAI) hollow fibers. For equivalent PEI concentrations, PAI functionalized with lower molecular weight PEI exhibit higher CO2 capacities (see picture). Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.