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In recent years, there has been growing interest in adsorbents with high surface area, high porosity, high stability and high selectivity for CO2 adsorption. By the incorporation of the additive on the supports such as zeolite, silica, and carbon, the physicochemical properties of the adsorbent and CO2 adsorption performance can be enhanced. In this review, we focus on the overview of bifunctional materials (BFMs) for CO2 adsorption. The findings of this study suggests that the high surface area and high porosity of the support provide a good medium for high dispersion and accessibility of additives (amine or metal oxide), enhancing the CO2 adsorption efficiency. The excessive additive however may lead to a decrease of CO2 adsorption performance due to pore blockage and the decrease of active sites for CO2 interactions. The synergistic relationship of the supporting material and additive is significant towards the enhancement of CO2 adsorption.