Polyacrylonitrile-based activated carbon fibers (ACFs), modified using potassium hydroxide (KOH) or tetraethylenepentamine (TEPA), were investigated for carbon dioxide (CO2) adsorption, which is one of the promising alleviation approaches for global warming. The CO2 adsorption isotherms were measured, and the values of isosteric heat of adsorption were calculated. The results showed that the KOH-modified ACFs exhibited a great deal of pore volume, and a specific surface area of 1565 m(2)/g was obtained. KOH activation made nitrogen atoms easily able to escape from the surface of ACFs. On the other hand, the surface area and pore volume of ACFs modified with TEPA were significantly reduced, which can be attributed to the closing or blocking of micropores by the N-groups. The CO2 adsorption on the ACF samples was via exothermic reactions and was a type of physical adsorption, where the CO2 adsorption occurred on heterogeneous surfaces. The CO2 uptakes at 1 atm and 25 degrees C on KOH-activated ACFs reached 2.74 mmole/g. This study observed that microporosity and surface oxygen functionalities were highly associated with the CO2 uptake, implying the existence of O-C coordination, accompanied with physical adsorption. Well cyclability of the adsorbents for CO2 adsorption was observed, with a performance decay of less than 5% over up to ten adsorption-desorption cycles.