<p>Hollow noble microspheres have garnered considerable interest owing to their potential applications in fields such as catalysis, electronics, and chemical detection. However, their inherent brittleness remains a critical limitation, significantly restricting their practical use in broader applications. In this work, we report a scalable methodology for the fabrication of vesicle-like polymer-silver composite microspheres with excellent toughness. The process begins with dispersion polymerization to produce uniform polystyrene (PS) microspheres, which are subsequently sulfonated to facilitate the electrostatic adsorption of Sn²⁺ ions. This is followed by the chemical reduction of [Ag(NH₃)₂]⁺, enabling the formation of well-defined core-shell SPS/Ag composite microspheres with tunable shell thickness through multiple reduction steps. Finally, the core template is removed using DMF solvent, resulting in vesicle-like SPS@Ag composite microspheres. Such hollow microspheres exhibit excellent toughness due to the presence of SPS within the silver membrane. Moreover, the surface-enhanced Raman scattering (SERS) performance of these microspheres is influenced by the thickness of the silver membrane. The findings of this study demonstrate their potential for the development of highly efficient SERS substrates, with broad application in analytical chemistry, sensing technologies, and catalytic processes.</p>