Nitrogen-enriched nanoporous polytriazines (NENPs) have been synthesized by ultrafast microwave-assisted condensation of melamine and cyanuric chloride. The experimental conditions have been optimized to tune the textural properties by synthesizing materials at different times, temperatures, microwave powers, and solvent contents. The maximum specific surface area (SA(BET)) of 840 m(2) g(-1) was estimated in the sample (NENP-1) synthesized at 140 degrees C with a microwave power of 400 W and reaction time of 30 min. One of the major objectives of achieving a large nitrogen content as high as 52 wt % in the framework was realized. As predicted, the nitrogen amelioration has benefitted the application by capturing a very good amount of CO2 of 22.9 wt % at 273 K and 1 bar. Moreover, the CO2 storage capacity per unit specific surface area (per m(2) g(-1)) is highest among the reported nanoporous organic frameworks. The interaction of the CO2 molecules with the polytriazine framework was theoretically investigated by using density functional theory. The experimental CO2 capture capacity was validated from the outcome of the theoretical calculations. The superior CO2 capture capability along with the theoretical investigation not only makes the nanoporous NENPs superior adsorbents for the energy and environmental applications but also provides a significant insight into the fundamental understanding of the interaction of CO2 molecules with the amine functionalities of the nanoporous frameworks.