Porous carbons have attracted much attention for their novel application in gas storage. In this study, porous graphite nano-fiber (PGNFs)-based graphite nano fibers (GNFs) were prepared by KOH activation to act as adsorbents. The GNFs were activated with KOH by changing the GNF/KOH weight ratio from 0 through 5 at 900°C. The effects of the GNF/ KOH weight ratios on the pore structures were also addressed with scanning electron microscope and N2 adsorption/desorption measurements. We found that the activated GNFs exhibited a gradual increase of CO2 adsorption capacity at CK-3 and then decreased to CK-5, as determined by CO2 adsorption isotherms. CK-3 had the narrowest micropore size distribution (0.6–0.78 nm) among the treated GNFs. Therefore, KOH activation was not only a significant method for developing a suitable pore-size distribution for gas adsorption, but also increased CO2 adsorption capacity as well. The study indicated that the sample prepared with a weight ratio of ‘3’ showed the best CO2 adsorption capacity (70.8 mg/g) as determined by CO2 adsorption isotherms at 298 K and 1 bar.