A topologically mediated synthesis of porous boron nitride aerogel has been experimentally and theoretically investigated for carbon dioxide (CO₂) uptake. Replacement of the carbon atoms in a precursor aerogel of graphene oxide and carbon nanotubes was achieved using an elemental substitution reaction, to obtain a boron and nitrogen framework. The newly prepared BN aerogel possessed a specific surface area of 716.56 m²/g and exhibited an unprecedented twentyfold increase in CO₂ uptake over N₂, adsorbing 100 cc/g at 273 K and 80 cc/g in ambient conditions, as verified by adsorption isotherms via the multipoint Brunauer-Emmett-Teller (BET) method. Density functional theory calculations were performed to give hints on the mechanism of such high selectivity of CO₂ over N₂ adsorption in BN aerogel, which may be due to the interaction between the intrinsic polar nature of B-N bonds and the high quadrupole moment of CO₂ over N₂.