A new bifunctional heterogeneous catalyst system was developed by immobilization of pyridinium-based ionic liquid on Zn-MOF-NH2 to produce an IL-supported Zn-MOF-NH2 catalyst. The dual-functional one-component system, including both Lewis acid sites and IL functional sites, showed high catalytic activity for the CO2-epoxide cycloaddition reactions under mild solvent-free conditions. Different techniques such as FE-SEM, EDX, FT-IR, XRD, and BET were applied to characterize of the as-prepared catalyst. This efficient low-leaching catalyst system is separated by centrifugation and can be reused successfully for four successive cycles without altering the catalytic activity in CO2 epoxidation to cyclic carbonates. Due to the wide variety seen in both metal–organic frameworks (MOFs) and ionic liquids (ILs), we believe that this research represents a significant step forward in the potential applications of synthetic modification methods within MOFs.