This study comprehensively examined the structural, optical, and dielec. properties of Pb3O4-Bi2O3-B2O3 glass-ceramics, doped with varying Ag2O concentrationsXRD and SEM analyses revealed the embedding of non-centrosym. Ag2BiO3 ferroelec. crystals (0.6-1.0 μm), whose properties are modeled using GGA and LDA approximations within the Pnn2 space group, aligning with exptl. data.XPS highlights the presence of Ag+/Ag0 and Bi3+/Bi5+ states, while FTIR spectroscopy indicates increasing structural disorder with up to 0.2 mol% Ag2O.Optical absorption identifies Ag+-Ag0 pairs, and dielec. measurements show an increase in permittivity and a.c. conductivity, with impedance decreasing up to 0.2 mol% Ag2O.Notably, 0.2 mol% Ag2O optimizes structural reorganization and dielec. performance, enhancing the material′s suitability for spin-orbitronics, optoelectronics, and solid-state batteries.The findings establish these glass-ceramics as next-generation materials for advanced technol. applications.