<p>As a critical index for heavy metal toxicity, the quantitative detection of silver ions (Ag⁺) is essential for health assessment and environmental monitoring. A sensing platform based on composite gold nanoclusters with dual emissions located in the near-infrared (NIR) range has been constructed for highly sensitive Ag⁺ quantification. Dual-emissive glutathione-functionalized gold nanoclusters (GSH-AuNCs) were first synthesized via a one-pot hydrothermal method. Then, the weak NIR emissions were effectively enhanced by introducing thiolated β-cyclodextrin to regulate the surface ligands of clusters and by ZIF-8 encapsulation to allow the spatial nanoconfinement effect. The GSH-AuNCs nanocomposite exhibited dual-channel emission peaked at 610&#xa0;nm and 810&#xa0;nm under 437&#xa0;nm excitation. Compared with the native clusters, the fluorescent emissions were enhanced with total factors of 6.86-fold at 610&#xa0;nm and 2.32-fold at 810&#xa0;nm. The sensing nanocomposite can specifically complex with Ag⁺ by the surface thiol groups and β-cyclodextrin cavities on clusters. The interaction between the fluorescent composite and Ag⁺ changed the ligand-to-metal charge transfer (LMCT) of the clusters and caused fluorescence enhancement at 610&#xa0;nm and quenching at 810&#xa0;nm. This opposite variation trend in the fluorescence intensities gives the possibility of constructing a ratiometric fluorescent probe for Ag⁺ detection. The dual-emission intensity ratio (F₆₁₀/F₈₁₀) demonstrates a quantitative relationship with Ag⁺ concentration (C_Ag+). The sensing system possesses a linear response range of 0.02~5.00&#xa0;μmol/L in pH 8.5 buffer, achieving a detection limit of 11.6&#xa0;nmol/L (S/N = 3). Measurement results of real serum and water samples confirmed that the sensing platform had good accuracy and exceptional anti-interference capability for Ag⁺ detection.</p> Graphical Abstract <p>Schematic synthesis of GSH-AuNCs, GSH-AuNCs@β-CD/ZIF-8 assembly, and the fluorescence sensing of Ag⁺.</p> <p></p>