Serials of pitch based spherical activated carbons (PSACs) were prepared and used as adsorbent for CO2 adsorption from flue gases. The results indicate that the ultrafine micropores (< 1 nm) are effective pores for CO2 adsorption, and the equilibrium adsorption capacity of CO2 has a linear relationship with the specific surface area of ultrafine micropores (S (< 1 nm)) The adsorption capacity of CO2 can obtain 1.12 mmol/g at 15 kPa and 30 degrees C on one of PSAC sample due to its high S (< 1 nm) (845 m(2)/g). Because the molecular CO2 can be polarized into polar molecules and has four kinds of adsorption configuration, the adsorption selectivities of CO2 vs. N-2 and O-2 are 86.99% and 69.91%, respectively. When the combined Electric Swing Adsorption and Vacuum Swing Adsorption were applied for CO2 desorption, about 100% desorption efficiency can be obtained, the desorption rate is twice of that with Temperature Swing Adsorption (TSA) and the energy consumption is only 69% of that with TSA. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.