In this study, polyacrylonitrile (PAN)-based porous carbon nanofibers were prepared from PAN polymer solution by electrospinning and KOH activation with various concentrations, and the characterization of pore structures and carbon dioxide adsorption was investigated. Manufactured PAN-based activated carbon nanofibers tend to decrease diameter and increase surface oxygen functional groups depending on the increasing concentration of KOH solution. In addition, according to the results of nitrogen adsorption for pore properties analysis, it indicated increase of the specific surface area in conformity with increasing concentration of KOH solution. Micropore volume of treated activated carbon nanofibers (ANCF) by 4 M KOH was the largest compared with other samples and mesopore volume of treated ANCF by 8 M KOH was the largest volume, respectively. The concentration of KOH effects textural and surface properties, as represented by BET and XPS, which enhance carbon dioxide adsorption capacity at 0 and 25 degrees C.