Porous carbon materials are considered to be one of the most promising candidates for CO2 capture due to their low cost,high surface area,high thermal and chemical stability and excellent performance in CO2 capture.[1,2] Another high-performance CO2 adsorption material Cu3(BTC)2 is usually obtained as finely dispersed powders.[3] In order to unite the performance features of monolithic porous carbon and Cu3(BTC)2,herein,we tend to investigate the synthesis of such composite materials composed of HCM and Cu3(BTC)2 for the application of CO2 capture.Cu3(BTC)2@HCM composites were synthesized by a step-by-step impregnation and crystallization method.This is the first report on the utilization of the free pore space of hierarchical porous carbon monolith for the growth of Cu3(BTC)2 crystallites.The obtained composites were characterized by different means such as SEM,XRD,FT-IR,TG-DSC,equilibrium CO2 and N2 adsorption isotherms at 25 ℃,and dynamic breakthrough separation experiments.The composites show high CO2 adsorption capacity at ambient conditions and can be regenerated at room temperature.When volumetric adsorption capacity is the major concern,such Cu3(BTC)2@HCM composite can meet this demand by showing remarkable increment in CO2 adsorption on a volumetric basis.