The objective of this research was to develop a new high-performance CO2 adsorbent with a simple method. Amine hybrid resorcinol-formaldehyde/silsesquioxane composite aerogel (AH-RFSA) was developed through polymeric sal-gel process and supercritical drying (SCD) technique. CO2 adsorption performances of AH-RFSA in 1% CO2 gas mixture (CO2 + N-2) were investigated. A rise in adsorption temperature negatively affects the total CO2 adsorption capacity of Al-RFSA. However, the useful adsorption capacity does not change with adsorption temperature. Water is more positive to useful CO2 adsorption capacity than to total CO2 adsorption capacity. The total CO2 adsorption capacity achieved with the new adsorbent at 30 degrees C under dry and humid 1% CO2 is 3.57 and 4.43 mmol/g, respectively. The useful CO2 adsorption capacity for complete removal of CO2 from 1% CO2 is as high as 3.56 mmol/g. The adsorbent preparation method is inspiring and its resulting adsorbent is exceptional in capacity and regenerability. (C) 2015 Elsevier Ltd. All rights reserved.