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Herein, a study on the dielectric properties of ZnO–P2O5–SeO2 glass ceramics containing varied contents of Ag2O is presented. Structural analysis of the samples by X‐ray diffraction, transmission electron microscopy, differential scanning calorimetry, Fourier transform infrared spectra, and optical absorption techniques indicated that the glasses are embedded with Ag3PO4, Ag2SeO3, and Zn3(PO4)2 anisotropic crystal phases along with Ag+ ions and Ag0 particles. Dielectric properties, ac conductivity (σac), and dielectric breakdown strength (DBS) are investigated as functions of Ag2O concentration. The results show the maximal concentration of Ag+ ions and Ag0 metallic particles in the sample containing 0.6 mol% of Ag2O. Dielectric parameters and (σac) increase with increasing Ag2O up to 0.6 mol%, while the DBS and electrical impedance decrease. The observed dipolar effects are quantitatively analyzed and possible dipoles are identified. Ionic contribution is predominant up to 0.6 mol% of Ag2O, beyond which the polaronic tunneling phenomenon prevails. These findings indicate that 0.6 mol% of Ag2O is the optimal concentration for using these glass ceramics as solid electrolytes in ionic batteries. Moreover, glass ceramics containing Ag2O beyond 0.6 mol% have exhibited larger polaronic conductivity, hence such glasses can be considered suitable candidates for electrodes in ionic batteries. [ABSTRACT FROM AUTHOR]