Bulk metallic glasses (BMGs) have unique microstructures that result in excellent physical and chemical properties. In this study, the impact of replacing Cu with Ag on the glass-forming ability (GFA), crystallization kinetics, mechanical properties, and corrosion resistance of the Zr₅₅Ti₃Cu_{32 - x} Al₁₀Ag _x (x = 0, 1, 1.5, 2, and 2.5; atomic fraction, %) BMGs in the Zr-Ti-Cu-Al alloy system was examined, aiming to develop new Ni/Be-free BMGs for biomedical applications. XRD and DSC analyses demonstrate that replacing Cu with appropriate amounts of Ag improves the GFA of the alloy system and considerably increases the crystallization activation energy (E_g, E_x, E_p1, and E_p2), thereby enhancing thermal stability. From a thermodynamic perspective, Ag has a large negative heat of mixing with other elements. Furthermore, the addition of Ag enhances the interaction among components and promotes chemical short-range ordering in liquid, which can improve the local filling efficiency and inhibit the long-range diffusion of atoms, thereby improving the GFA. At the atomic level, Ag exhibits a considerable atomic radius disparity with the primary constituents, and its inclusion can generate a proficient and localized stacking configuration, thereby achieving reduced internal energy and augmented viscosity and enhancing the GFA of Zr₅₅Ti₃Cu_{32 - x} Al₁₀Ag _x BMG. Mechanical property tests showed that the fracture strength increased with the increase of Ag content. In addition, the compressive deformation ability of Zr₅₅Ti₃Cu_{32 - x}Al₁₀Ag _x BMGs is improved by the addition of appropriate Ag. The compressive strain of the new Zr₅₅Ti₃Cu_30.5Al₁₀Ag_1.5 reaches 5.49%, which is 120% higher compared to the initial system. The addition of Ag may create local heterogeneity in the microstructure, allowing many secondary shear bands to appear during the expansion of the primary shear band, which increases the plasticity of the BMG. Electrochemical corrosion behavior analysis showed that the addition of appropriate Ag reduced the corrosion current density and increased the self-corrosion potential of Zr₅₅Ti₃Cu_{32 - x} Al₁₀Ag _x BMG. Moreover, Ag enhanced the biocorrosion resistance of Zr₅₅Ti₃Cu_{32 - x} Al₁₀Ag _x BMG in simulated body fluid and phosphate-buffered saline. Therefore, the new Zr-Ti-Cu-Al-Ag BMG system has shown great application potential as a biomedical material.