The oxyfluorination effects of activated carbon nanofibers (OFACFs) were investigated for CO2 storage. Electrospun CFs were prepared from a polyacrylonitrile/N,N-dimethylformamide solution via electrospinning and heat treatment. The electrospun CFs were chemically activated in order to generate the pore structure, and then oxyfluorination was used to modify the surface. The samples were labeled CF (electrospun CF), ACF (activated CF), OFACF-1 (O2:F2 = 7:3), OFACF-2 (O2:F2 = 5:5) and OFACF-3 (O2:F2 = 3:7). The functional group of OFACFs was investigated using X-ray photoelectron spectroscopy analysis. The C-F bonds formed on surface of ACFs. The intensities of the C-O peaks increased after oxyfluorination and increased the oxygen content in the reaction gas. The specific surface area, pore volume and pore size of OFACFs were calculated by the Brunauer–Emmett–Teller and density functional theory equation. Through the N2 adsorption isotherm, the specific surface area and pore volume slightly decreased as a result of oxyfluorination treatment. Nevertheless, the CO2 adsorption efficiency of oxyfluorinated ACF improved around 16 wt% due to the semi-ionic interaction effect of surface modificated oxygen functional groups and CO2 molecules.