<p>The development and synthesis of ligands with unique capacities to modify and improve the UiO-66-NH₂ framework have always attracted the attention of researchers. In this regard, we succeeded in synthesizing a new ligand, 1,4-phenylene bis(cyanoguanidine), from cyanoguanidine derivatives with crosslinking capacity. Then, to modify and improve the UiO-66-NH₂ framework, the synthesized ligand was used to introduce 1,4-phenylene bis(biguanide) into the framework via polymerization. Incorporation of a bidentate biguanide ligand into the UiO-66-NH₂ scaffold enhances the functionality of the framework by forming stable complexes with Cu(OAc)₂ and minimizing metal ion leakage during the reaction. Characterizations of the functionalized MOF were conducted using various techniques, including FTIR, FE-SEM, EDX, XRD, AAS, TGA, and N₂ adsorption–desorption, followed by catalytic evaluation of the composite. The synergistic effect between copper and zirconium resulted in outstanding performance of the nanocatalyst in synthesizing polyhydroquinoline and tetrahydrobenzo[b]pyran derivatives. The results obtained from the comparison of the synthesized nanocatalyst with UiO-66-NH₂@Cu(II), UiO-66-NH₂-BBG, and pure UiO-66-NH₂ showed that the improved catalytic performance of UiO-66-NH₂-BBG@Cu(II) can be attributed to the integration of the copper complex of the 1,4-phenylene bis(biguanide) ligand into the MOF structure. The modified UiO-66-NH₂ showed higher thermal stability than the parent UiO-66-NH₂. This nanohybrid demonstrated excellent recyclability and maintained its catalytic activity over five consecutive cycles without significant degradation.</p> Graphical Abstract <p></p>