Under diverse and dramatically different chemical environments, including organic solvents, an ionic-Liquid, and a deep eutectic solvent, a series of porous anionic framework materials that contain size-tunable, ion-exchangeable extraframework organic cations have been prepared. Even though a large fraction of the pore space is occupied with charge-balancing cations, some of these materials exhibit a very high gas uptake capacity (e.g., 70.6 cm(3)/g for CO2 at 1 atm and 273 K), suggesting that the charged anionic framework and extraframework cations may help to enhance the gas adsorption.