Layered double hydroxides (LDHs) with a hierarchical mesostructure are successfully synthesized on mesoporous silica foams by simple impregnation and hydrothermal treatment. The as-synthesized LDH/silica foam nanocomposites show well-defined mesostructures with high surface areas, large pore volumes, and mesopores of 6-7 nm. The nanocomposites act as carbon dioxide (CO2) sorbents under simulated flue gas conditions. They also exhibit significantly enhanced CO2 capacities under high-pressure conditions and high CO2/N2 and CO2/CH4 selectivities. Respect the hierarchy: Hierarchical mesoporous layered double hydroxide (LDH) nanocomposites with high surface areas and large pore volumes are synthesized by controlled hydrothermal growth of LDH precursors on a mesoporous silica foam. The as-synthesized nanocomposites exhibit a significantly enhanced capacity and selectivity towards carbon dioxide, making them very promising candidates for carbon dioxide (CO2) separation applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.