In this work, we examine the use of the amidoxime functional group grafted onto a hierarchical porous carbon framework for the selective capture and removal of carbon dioxide from combustion streams. Measured CO2/N2 ideal selectivity values for the amidoxime-grafted carbon were significantly higher than the pristine porous carbon with improvements of 65%. Though the overall CO2 capacity decreased slightly for the activated carbon from 4.97 mmol g−1 to 4.24 mmol g−1 after surface modification due to a reduction in the total surface area, the isosteric heats of adsorption increased after amidoxime incorporation indicating an increased interaction of CO2 with the sorbent. Total capacity was reproducible and stable after multiple adsorption/desorption cycles with no loss of capacity suggesting that modification with the amidoxime group is a potential method to enhance carbon capture.