Poly(acrylic acid) (PAA)/poly(vinyl alcohol) (PVA) membrane was prepared for the facilitated transport of CO2. The carrier of CO2 was monoprotunated ethylenediamine and was introduced in the membrane by ion exchange. The ion-exchange capacity of the membrane was 4.5 meq/g, which was much higher than that of the Nafion 117 membrane. The membrane was highly swollen by the aqueous solution. Much higher selectivity of CO2 over N-2 and higher CO2 permeability were obtained in the PAA/PVA membrane than in the Nafion membrane because of the higher ion-exchange capacity and solvent content. The highest selectivity was more than 1900 when the CO2 partial pressure in the feed gas was 0.061 atm. Effects of ion-exchange capacity, membrane thickness, and annealing temperature in conditions of membrane preparation on membrane performance were investigated.