Conventional MCM-41 (M41), silica-pure pore-expanded MCM-41 (PM41), and Al-containing poreexpanded MCM-41 (PM41Ax) were synthesized from rice husk ash and tested as polyethyleneimine (PEI) supports for CO2 capture. Samples were characterized by small-angle X-ray diffraction, X-ray fluorescence spectroscopy, scanning electron microscopy, Fourier transform infrared spectroscopy, granulometric analysis, and nitrogen adsorption techniques. The PEI loading rate and CO2 adsorption-desorption performance were determined via thermogravimetric analysis. The effects of pore expansion, heteroatom Al incorporation, PEI loading rate, and Si/Al ratio on CO2 adsorption performance were examined. For the first time, the amount of PEI impregnated in PM41 was increased beyond 55 wt%, and the low-Si/Al-ratio PM41Ax support was used to load PEI in a novel procedure. Results show that at the same PEI loading rate, PM41 is always superior to M41 regarding adsorption capacity and adsorption rate. For a PEI loading rate >50 wt%, the superiority is amplified, reaching 15.9% and 21.3%, respectively. The use of the high-Al-containing PM41Ax support further increases adsorption capacity and adsorption rate by 13.4% and 9.6%, respectively. The presented reaction has a hybrid adsorption characteristic that includes both chemisorption and physisorption. Avrami’s fractional-order kinetic model describes the adsorption best. Over the entire time scale, the adsorption rate is determined by several kinetic diffusion-controlled processes. The intraparticle diffusion and equilibrium adsorption are two predominant rate-limiting steps, and their control ranges change with temperature. After five cycles of adsorption and desorption, the desorption ratio was as high as 99%, and the working capacity still retained 96.5% of the original capacity. In addition, the presence of water vapor increased the adsorption capacity of the adsorbents presented in this study. These advantages make them successful iin capturing CO2 in the post-combustion scenario.