Ion conducting materials of the AgI–Ag2O–V2O5 system were prepared at room temperature via mechanosynthesis. Their crystallographic structure, microstructure, local dynamics and thermal properties were monitored by X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman spectroscopy and differential scanning calorimetry (DSC), respectively. It was found that the prolonged ball-milling of mixtures described by formulae: (i) xAgI·0.25(100− x)(3Ag2O·V2O5), for 40≤ x ≤70, and (ii) xAgI·0.2(100− x)(3Ag2O·2V2O5), for 0≤ x ≤60, led to the formation of amorphous materials. DSC scans and Raman spectra indicate that the thermal events in the mechanosynthesized materials and their main constituting units are similar to those observed for the glasses of the same compositions, prepared by a standard melt-quenching technique.