Turning carbon dioxide (CO2) into valuable chemicals is one way of mitigating the environmental problem caused by the greenhouse gas. Cycloaddition of CO2 to epoxide to form cyclic carbonate is a promising route extensively researched in recent years. One focus has been the development of efficient catalysts to promote this reaction. Metal-organic frameworks (MOFs) are potential candidates owing to their high internal surface area and structural tunability to incorporate functional motifs. The talk introduces a new class of metal-cyclam-based MOFs exhibiting high CO2 update, excellent catalytic activity for the cycloaddition reaction, and good reusability. The structures of these new MOFs were determined by synchrotron X-ray powder diffraction, which was also employed to in situ characterize thermal stability of the MOFs and the interactions with guest molecules of CO2. The geometry of the MOFs, presenting open metal centers in the linkers and unsaturated metal notes, may find broad applications in heterogeneous catalysis.