In this work, we report the preparation of polyacrylonitrile (PAN)-based activated carbon nanofibers composited with different concentrations of reduced graphene oxide (rGO/ACNF) (1%, 5%, and 10% relative to PAN weight) by a simple electrospinning method. The electrospun nanofibers (NFs) were carbonized and physically activated to obtain activated carbon nanofibers (ACNFs). Texture, surface and elemental properties of the pristine ACNFs and composites were characterized using various techniques. In comparison to pristine ACNF, the incorporation of rGO led to changes in surface and textural characteristics such as specific surface area (SBET), total pore volume (Vtotal), and micropore volume (Vmicro) of 373 m2/g, 0.22 cm3/g, and 0.15 cm3/g, respectively, which is much higher than the pristine ACNFs (e.g., SBET = 139 m2/g). The structural and morphological properties of the pristine ACNFs and their composites were studied by Raman spectroscopy and X-ray diffraction (XRD), and field emission scanning electron microscopy (FE-SEM) respectively. Carbon dioxide (CO2) adsorption on the pristine ACNFs and rGO/ACNF composites was evaluated at different pressures (5, 10, and 15 bars) based on static volumetric adsorption. At 15 bar, the composite with 10% of rGO (rGO/ACNF0.1) that had the highest SBET, Vtotal, and Vmicro, as confirmed with BET model, exhibited the highest CO2 uptake of 58 mmol/g. These results point out that both surface and texture have a strong influence on the performance of CO2 adsorption. Interestingly, at p < 10 bar, the adsorption process of CO2 was found to be quite well fitted by pseudo-second order model (i.e., the chemisorption), whilst at 15 bar, physisorption prevailed, which was explained by the pseudo-first order model.