UTSA-16, The second highest porous MOF for CO2 capture, was for the first time employed for CO2 cycloaddition reaction. It combined the CO2 capture and conversion steps into one. Carbon dioxide was fixed and activated by potassium species decorated in the framework, prior to insertion into the active epoxides performed by the coordinated unsaturated metal sites Co. In the absence of co-catalyst, the catalyst showed activities to propylene oxide and some other epoxides under relatively mild conditions, performed true heterogeneous catalysis, could be reused five times without loss of catalytic activity.