MIL-101(Cr, Mg) is a promising metal organic framework (MOF) considering its moisture, thermal, and chemical stabilities. Piperazine-loaded polyacrylonitrile (PAN)/MIL-101(Cr, Mg) fiber mats were fabricated with different percentages of piperazine (10%, 20%, and 30%) in the polymer solution using an electrospinning technique. The PAN/MIL-101 fiber mats exhibited improved adsorption capacity and selectivity when combined with piperazine because of the improved affinity of CO2 molecules for the basic amine sites of piperazine. PAN/MIL-101–20% was selected as an optimum fiber mat owing to its high CO2 adsorption capacity (2.48 mmol/g) and selectivity (38), which are 2.4 and 2.9 times higher than those of the fiber mat without piperazine, respectively. The stability of the PAN/MOF fiber mat in humid air and NO2 gas and the results of ten adsorption-desorption experiments showed consistent CO2 capture performance.