A series of high-capacity, amine impregnated sorbents based on a cost-effective silica foam with ultra-large mesopores is reported. The sorbents exhibit fast CO2 capture kinetics, high adsorption capacity (of up to 5.8 mmol g−1 under 1 atm of dry CO2), as well as good stability over multiple adsorption–desorption cycles. A simple theoretical analysis is provided relating the support structure to sorbent performance.