The diffusion of CO2 and mobility of O-2-are the keys to capture of CO2 for CaO-based sorbents. We present a (Ce-Mn)-doped calcium-based sorbent, and investigate the effect of Ce and Mn incorporation on CO2 capture. Interaction between Ce and Mn promotes electron donation from Ca atom to surface oxygen atoms. The stronger the electrons transfer, the stronger interaction between CaO and CO2 is, thus improving CO2 adsorption. Electron transfer between Ce and Mn facilitates oxygen vacancy generation, which improves diffusion and mobility of O2-. In addition, CeO2 and Ca2MnO4 prevent CaO crystallite growth and agglomeration. The (Ce-Mn)-doped sorbents exhibited excellent long-term durability with carbonation capacity of about 0.61 g-CO2/g-ads after 40 cycles.