A highly efficient and stable solid adsorbent invoking a direct incorporation of tetraethylenepentamine (TEPA) onto the as-synthesized mesocelullar silica foam (MSF) has been developed for CO2 capture. Unlike most amine-functionalized silicas, which typically exhibit CO2 adsorption capacities less than 2.0 mmol/g, such organic template occluded mesoporous silica-amine composites exhibited remarkably high CO2 uptake as high as 4.5 mmol/g at 348 K and 1 atm. Moreover, notable increases in CO2 adsorption capacities of the composite materials were observed when in the presence of humidity. Durability test performed by cyclic adsorption-desorption revealed that such adsorbents also possess excellent stability, even though a slight decrease in adsorption capacity over time was observed.