In this work, nitrogen-doped bamboo-based activated carbon (NBAC) was in situ synthesized from simply blending bamboo charcoal (BC) with sodamide (SA, NaNH2) powders and heating with a protection of nitrogen flow at a medium temperature. The elemental analysis and X-ray photoelectron spectra of as-synthesized NBAC showed quite a high nitrogen level of the simultaneously activated and doped samples; an abundant pore structure had also been determined from the NBACs which has a narrow size distribution of micropores (<2 nm) and favorable specific surface area that presented superb adsorption performance. The fcarbon dioxide (CO2) adsorption of the NBACs was measured at 0 °C and 25 °C at a pressure of 1 bar, whose capture capacities reached 3.68–4.95 mmol/g and 2.49–3.52 mmol/g, respectively, and the maximum adsorption could be observed for NBACs fabricated with an SA/BC ratio of 3:1 and activated at 500 °C. Further, adsorption selectivity of CO2 over N2 was deduced with the ideal adsorbed solution theory ((IAST), the selectivity was finally calculated which ranged from 15 to 17 for the NBACs fabricated at 500 °C). The initial isosteric heat of adsorption (Qst) of NBACs was also determined at 30–40 kJ/mol, which suggested that CO2 adsorption was a physical process. The results of ten-cycle adsorption-desorption experimentally confirmed the regenerated NBACs of a steady CO2 adsorption performance, that is, the as-synthesized versatile NBAC with superb reproducibility makes it a perspective candidate in CO2 capture and separation application.