Developing efficient catalysts for organic pollutants degradation is crucial for remediating the current severe water environment, yet remains a great challenge. Herein, we report silver nanoparticles immobilized on an amine-functionalized metal-organic framework (MOFs) (Ag/UiO-66-NH₂) as a robust catalyst for the reduction of 4-nitrophenol (4-NP). The fabricated Ag/UiO-66-NH₂ catalyst exhibits the merits of superior activities (high turnover frequency (TOF) 3.2 × 10⁴ h^–1 and k value 6.9 × 10^–2 s^–1), cost-effectiveness under the lowest NaBH₄ concentration (n_[NaBH4]/n_[4-NP], 200), outstanding cyclability (10 recycling runs), and observable long-term durability, significantly outperforming previously reported catalytic system. The excellent degradation efficiency is ascribed to the favorable microenvironment modulation of unique MOF structure, which regulates the intrinsic properties of active sites and improves the electron-transfer process. Notably, the Ag/UiO-66-NH₂ also promotes the catalytic degradation of several organic pollutants at room temperature and hence could find a broad application for water remediation. This work offers a new avenue for the development of high-performance MOF-based catalysts with excellent activity and durability.