Carbon capture, utilization and storage (CCUS) is one of the most interesting mitigation strategies towards climate change. More specifically, biocatalytic utilization of captured CO2 could outperform traditional chemical routes in terms of sustainability and selectivity. However, the high Henry constant in water, together with unfavorable thermodynamics, challenge the feasibility of the reversible sequestration and chemical utilization of the gas. To overcome these issues, the design of hierarchical microporous-macroporous materials for the selective capture and enzymatic transformation of CO2 to valuable chemicals were proposed. Specifically, the immobilization of different formate dehydrogenase (FDHs) enzymes over Co2+-agarose macroporous carriers were studied and optimized in terms of protein load. Produced biocatalysts were employed in gas-saturated media for the reduction of CO2 to formic acid. Then, microporous metal organic framework (MOF) with high surface area (?2000 m2/g) were synthesized to selectively capture CO2 over N2.The assembly of the two modules will be provided, with the microporous nanostructures acting as carbon reservoirs for the macroporous biocatalytic domain. This strategy would provide high local CO2 concentration, allowing the biocatalysts to perform in out-ot-equilibrium conditions.