In this work, bimodal (mesa-macro) porous silicas with different mesopore diameters synthesized by using rice husk ash as a low-cost silica source and chitosan as a natural template were used as a polyethyleneimine (PEI) support for CO2 capture. Unimodal porous silica supports with equivalent mesopore diameters to bimodal porous silica supports have been prepared for purpose of comparison. Effects of different PEI contents (10, 20, 30, 40 and 50 wt%) on CO2 sorption capacity have been systematically investigated. The porous silica supports and the PEI-loaded porous silica supports were characterized by N-2-sorption analysis, scanning electron microscopy, Fourier transform infrared spectroscopy and thermal gravimetric analysis. CO2 sorption measurements of all PEI-loaded porous silica supports were performed at different adsorption temperatures (60, 75, 85, 90, 95 and 105 degrees C). At low PEI contents (10-20 wt%), the CO2 sorption of all adsorbents was found to decrease as a function of adsorption temperature, which was a characteristic of a thermodynamically-controlled regime. A transition from the thermodynamically-controlled regime to a kinetically-controlled regime was found when the PEI content was increased up to 30 wt% for PEI-loaded unimodal porous silicas and 40 wt% for PEI-loaded bimodal porous silicas. At high PEI contents (40-50 wt%), the CO2 capturing efficiency of the PEI-loaded bimodal porous silicas was found to be considerably greater than that of the PEI-loaded unimodal porous silicas, indicating that most of the amine groups of PEI molecules loaded on the unimodal porous silica supports was useless, and thus the appeared macroporosity of the bimodal porous silica supports could provide a higher effective amine density to adsorb CO2. (C) 2012 Elsevier B.V. All rights reserved.