The present work aims at preparing the EDTA-Zn(II) complex-supported on the amine-functionalized MIL-101(Cr) MOF-as a new and effective heterogenized catalyst. The optimization of the hydrothermal process shows that 120 °C is the best condition to grow the MIL-101(Cr)-NH MOF crystals. Moreover, regarding the use of the postsynthetic modification (PSM) method, hexadentate EDTA was grafted on this support via a simple aminolysis process before further coordinating it with Zn ions to create the corresponding Zn(II) catalytic complex. The catalytic activity of this compound was then investigated in the context of a one-pot synthesis of polyhydroquinolines. This approach has a number of advantages including the following: the use of a solvent that is not hazardous, applying a porous catalyst that is inexpensive, secure, and recyclable; rapid reaction times, high levels of efficiency, and the simplicity of MOF catalyst separation. Accordingly, the process in question can be given the label of "green chemistry".