A facile functionalization assisted by the structural attributes of PCN-333 has been studied while maintaining the integrity of the parent MOF including ultralarge pores, chemical robustness, and crystallinity. Herein we thoroughly analyzed ligand exchange phenomena in PCN-333 and demonstrate that the extent of exchange can be tailored by varying the exchange conditions as potential applications may require. Through this method a variety of functional groups are incorporated into PCN-333. To further show the capabilities of this system introduction of a BODIPY fluorophore as a secondary functionality was performed to the functionalized framework via a click reaction. We anticipate the PCN-333 with functional anchor can serve as a stable platform for further chemistry to be explored in future applications.