Structural and electrical properties of the ternary ionic–electronic conducting glass system xAgI–(1 − x)[0.67Ag2O–0.33V2O5], where x = 0.4, 0.5, 0.6, 0.7, and 0.8 were studied for emphasizing the influence of silver iodide concentration on the transport properties of the based vanadate glasses. The glasses were prepared by melt quenching technique and characterized using X-ray diffraction (XRD), FTIR spectra, and differential thermal analysis (DTA). Electrical conductivity (σ), dielectric constant (ε′), dielectric loss (ε″), and impedance spectra (Z′-Z″) were studied for all samples. All glasses showed a mixed ionic–electronic conductance with a high ionic conductivity for the sample with x = 0.7. The electronic contribution to the total conductivity and the ionic (t i) and electronic transport numbers (t e) were determined for each glass sample using Wagner’s DC polarization technique. The variation in electrical properties with each of composition, temperature, and frequency was analyzed and discussed. Graphical Abstract AgI dopant (0.7 mol) created more opened vanadate network structure and enhanced both ion migration and orientation and as a result showed a high DC conductivity and ionic transfer number at room temperature.