Adsorption is considered to be one of the more promising technologies for capturing CO2 from flue gases. The efficient adsorption of CO2 at low partial pressures, associated with post-combustion capture, require chemical type adsorbents containing basic amine functional groups. It has been demonstrated that amine polymers, for example polyethylenimine (PEI), immobilised on various porous substrates, silica, zeolites and fly ash, are effective adsorbents for CO2. When considering the use of adsorption for large scale CO2 capture, the ease of regeneration and the lifetime of the adsorbents are critical factors in determining their efficiency, cost and therefore feasibility for use. In this paper two approaches, thermal swing adsorption (TSA) cycles over a range of temperatures and time in an atmosphere of CO2 and thermally assisted pressure swing desorption, are explored for the regeneration of the PEI based adsorbents. The Carbon Trust and EPSRC (Advanced Research Fellowship EP/C543201/1) Peer reviewed