Recently, amine-functionalized materials as a prospective chemical sorbent for post combustion CO₂ capture have gained great interest. However, the amine grafting for the traditional MCM-41, SBA-15, pore-expanded MCM-41 or SBA-15 supports can cause the pore volume and specific surface area of sorbents to decrease, significantly affecting the CO₂ adsorption-desorption dynamics. To overcome this issue, hierarchical porous silica with interparticle macropores and long-range ordering mesopores was prepared and impregnated with pentaethylenehexamine. The pore structure and amino functional group content of the modified silicas were analyzed by scanning electron microscope, transmission electron microscope, N₂ adsorption, X-ray powder diffraction, and Fourier transform infrared spectra. Moreover, the effects of the pore structure as well as the amount of PEHA loading of the samples on the CO₂ adsorption capacity were investigated in a fixed-bed adsorption system. The CO₂ adsorption capacity reached 4.5 mmol CO₂/(g of adsorbent) for HPS−PEHA-70 at 75 °C. Further, the adsorption capacity for HPS-PEHA-70 was steady after a total of 15 adsorption-desorption cycles.