In this work, nitrogen-doped porous carbons (NACs) were fabricated as an adsorbent by urea modification and KOH activation. The CO adsorption mechanism for the NACs was then explored. The NACs are found to present a large specific surface area (1920.72–3078.99 m ·g ) and high micropore percentage (61.60%–76.23%). Under a pressure of 1 bar, sample NAC-650-650 shows the highest CO adsorption capacity up to 5.96 and 3.92 mmol·g at 0 and 25 °C, respectively. In addition, the CO /N selectivity of NAC-650-650 is 79.93, much higher than the value of 49.77 obtained for the nonnitrogen-doped carbon AC-650-650. The CO adsorption capacity of the NAC-650-650 sample maintains over 97% after ten cycles. Analysis of the results show that the CO capacity of the NACs has a linear correlation ( = 0.9633) with the cumulative pore volume for a pore size less than 1.02 nm. The presence of nitrogen and oxygen enhances the CO /N selectivity, and pyrrole-N and hydroxy groups contribute more to the CO adsorption. Fourier transform infrared spectra analysis indicates that CO is adsorbed onto the NACs as a gas. Furthermore, the physical adsorption mechanism is confirmed by adsorption kinetic models and the isosteric heat, and it is found to be controlled by CO diffusion. The CO adsorption kinetics for NACs at room temperature and in pure CO is in accordance with the pseudo-first-order model and Avramís fractional-order kinetic model.