CO2 is considered as the primary greenhouse gas, resulting in a series of serious environmental problems that affect people's life and health. Carbon capture and sequestration has been implemented as one of the most appealing pathways to control and use CO2. Here, we rationally integrate various functional sites within the confined nanospace of a microporous metal–organic framework (MOF) material, which is constructed by mixed‐ligand strategy based on metal‐adeninate vertices. It not only exhibits excellent stability but also can efficiently transform CO2 and epoxides to cyclic carbonates under mild and cocatalyst‐free conditions. Additionally, this catalyst shows extraordinary recyclability for the CO2 cycloaddition reaction.

An exceptionally stable metal–organic framework (MOF) can be rationally constructed by mixed‐ligand strategy, based on ZnII‐adeninate vertices and 2,2′‐dimethyl‐4,4′‐azodibenzoate linkers. The 3D porous MOF not only has a certain amount of CO2 sorption ability but contains rich Lewis acid (ZnII) and basic (−NH2) sites within the confined nanospace. As a result, it can serve as a high‐efficiency heterogeneous catalyst for cycloaddition of CO2 with epoxides to afford cyclic carbonates under mild conditions without solvent or cocatalyst. Moreover, the remarkable stability results in its excellent recyclability for catalytic reactions. More information can be found in the Full Paper by C.‐P. Li, M. Du, et al. on page 11474.