Abstract: The recovery of precious metals (PMs) from secondary resources is critical for addressing global supply-chain vulnerabilities and sustainable resource utilization. This review systematically examines the transformative potential of metal–organic frameworks (MOFs) as next-generation adsorbents for PM recovery, focusing on their synthesis, functionalization, and multiscale adsorption mechanisms. We critically analyze conventional pyrometallurgical and hydrometallurgical methods and highlight their limitations in terms of selectivity, energy consumption, and secondary pollution. In contrast, MOFs offer tunable porosity, abundant active sites, and tunable surface chemistry, enabling efficient PM capture via synergistic physical and chemical adsorption. Advanced modification techniques, including direct synthesis and post-synthetic modification, are reviewed to propose strategies for enhancing the adsorption kinetics and selectivity for Au, Ag, Pt, and Pd. Key structure–property relationships are established through multiscale characterization and thermodynamic models, revealing the critical roles of hierarchical porosity, soft donor atoms, and framework stability. Industrial challenges, such as aqueous stability and scalability, are addressed via Zr–O bond strengthening, hydrophobic functionalization, and support immobilization. This study consolidates the experimental and theoretical advances in MOF-based PM recovery and provides a roadmap for translating laboratory innovations into practical applications within the circular-economy framework.