Carbon nanofibers were electrospun from melamine-blended polyacrylonitrile (MACNFs), for improved indoor level CO2 removal of the fibrous adsorbent. The dopant (melamine) was used to provide free and basic nitrogen functionalities, as well as to shorten the fabrication time of the nanofibers. Upon final CO2 activation of the nanofibers, the specific surface area and microporosity were enhanced. As per chemical properties, the surface basicity was improved through the significant tethering of pyridone. The sample, MACNF-7 (10 mL polymer solution doped with 0.7 g melamine) provides the optimum doping ratio to achieve the highest CO2 adsorption capacity of 3.15 mmol/g. This performance was based on simultaneous and just-adequate improvement of the microporosity (physical) and surface basicity (chemical) of the adsorbent. However, the selective adsorption of CO2, in a binary mixture with nitrogen, showed the predominance of the improved chemical properties over microporosity; the highest CO2 selective capture (1.22 mmol/g) was exhibited by applying CO2 : N2 of 0.15 : 0.85., with the selectivity fold of 58.19 at 273 K. In a 5-fold regeneration test, a stable and robust performance was achieved throughout the five cycles.