<p>Noble metal nanoclusters (MNCs), intrinsically possessing atomically precise structures and tunable compositions, have emerged as promising candidates for advanced catalysis, sensing, and energy-related applications. However, their practical utilization is severely hampered by rapid oxidation-induced structural degradation and ligand detachment under ambient conditions, leading to inevitable aggregation into larger particles during storage or catalytic process. Here, we developed a redox-mediated stabilization strategy by integrating ultrasmall Au₂₅ NCs with amine-functionalized metal-organic frameworks (MOF). The abundant and uniformly dispersed amine groups as reductive reagents to suppress the oxidation of Au atoms while simultaneously reinforcing thiol-terminated ligands anchoring through dynamic coordination processes. The dual stabilization strategy enables Au₂₅ NCs to maintain their initial ultrasmall particle sizes and structural integrity under ambient storage and light irradiation processes. Furthermore, the engineered type-II heterojunction between Au₂₅ NCs and UiO-66-NH₂ significantly enhances visible-light harvesting capacity and charge separation efficiency, thus achieving efficient activation of O₂ to form reactive oxygen species (ROS). The Au₂₅/UiO-66-NH₂ composites exhibit outstanding photocatalytic antibacterial activity and durability, achieving 99.999% bacterial inactivation efficiency against <i>Escherichia coli</i> (<i>E. coli</i>) within 40 min under visible light while retaining the high efficacy after five reuse cycles. The integration of Au₂₅/UiO-66-NH₂ into wearable fabrics underscores its significant potential to provide continuous antibacterial protection. This work establishes amine-functionalized MOFs as universal redox-active supports for stabilizing metastable MNCs and provides a versatile platform for designing durable photocatalytic systems in environmental and biomedical applications.</p>