<p>Metal-Organic Frameworks (MOFs) have attracted widespread attention for their applications in water-related contexts. A comprehensive understanding of the molecular-level interactions between water and MOFs is crucial for guiding molecular design and optimizing water-related applications. Water can act as a passive guest, interacting weakly with open metal sites or polar linkers without altering the framework, or as a reactive species that cleaves the dative bonds between inorganic clusters and organic linkers, leading to irreversible degradation. In this work, we uncover a significant impact of water on the metal-linker linkage in UiO-66, a prototype MOFs which is considered highly stable with water. The adsorption of water molecules in UiO-66 results in the displacement of firmly attached carboxylate groups of the linker, thereby transforming them into dangling carboxylate groups. These dangling groups are stabilized by water molecules and μ₃-OH through hydrogen bonding. Remarkably, this structural transformation is reversible upon water removal. These findings were elucidated through the integration of multidimensional solid-state NMR, cutting-edge dynamic nuclear polarization (DNP) techniques, and computational calculations. By challenging conventional wisdom, our research has introduced a reversible molecular structure evolution scenario, redefining the understanding of water-MOF interactions.</p>