This work aims to optimize the structural features of hierarchical porous carbon monolith (HCM) by incorporating the advantages of metal-organic frameworks (MOFs) (Cu₃(BTC)₂) to maximize the volumetric based CO₂ capture capability (CO₂ capacity in cm³ per cm³ adsorbent), which is seriously required for the practical application of CO₂ capture. The monolithic HCM was used as a matrix, in which Cu₃(BTC)₂ was in situ synthesized, to form HCM-Cu₃(BTC)₂ composites by a step-by-step impregnation and crystallization method. The resulted HCM-Cu₃(BTC)₂ composites, which retain the monolithic shape and exhibit unique hybrid structure features of both HCM and Cu₃(BTC)₂, show high CO₂ uptake of 22.7 cm³ cm⁻³ on a volumetric basis. This value is nearly as twice as the uptake of original HCM. The dynamic gas separation measurement of HCM-Cu₃(BTC)₂, using 16% (v/v) CO₂ in N₂ as feedstock, illustrates that CO₂ can be easily separated from N₂ under the ambient conditions and achieves a high separation factor for CO₂ over N₂, ranging from 67 to 100, reflecting a strongly competitive CO₂ adsorption by the composite. A facile CO₂ release can be realized by purging an argon flow through the fixed-bed adsorber at 25 °C, indicating the good regeneration ability.