This study presents a simple, rapid, highly efficient, and environmentally friendly technique for recovering silver microstructures from spent button batteries. The technique exploits the reducing ability of H₂O₂ to convert silver sources into high-purity silver at the microscopic scale. The influence of polymeric stabilizers (PVP and PVA) on the formation of silver microstructures was elucidated. The results revealed that polymeric stabilizers play a crucial role in controlling the growth of silver particles at the microscopic level. Specifically, PVP affords a homogeneous silver microplate, whereas PVA facilitates the formation of isotropic spherical microparticles. Additionally, the effect of the molecular weight (Mw) of the stabilizers on the silver particles was examined. The Mw of PVP significantly impacts its anti-aggregation properties. Similarly, the Mw of PVA affects the formation of silver microstructures. The high purity of the recovered silver microstructures was verified by EDX and XRD. Finally, the optimal recovery conditions were implemented to recover silver from button batteries. These battery residues were successfully transformed into highly pure silver microplates and microspheres using those respective polymeric stabilizers. The further application is to produce a flexible conductive material by combining recovered silver film with various morphologies on a flexible polymer. This protocol aims to manage the sensitivity of electrical conductivity and resistance when a developed substrate is subjected to mechanical strain, such as stretching, bending, and twisting.