Glasses of the formula 30Ag2O⋅xB2O3⋅(70–x)TeO2 (0 ≤ x ≤ 70 mol%) were prepared under normal conditions, followed by FTIR spectroscopy, density, molar volume, XRD, SEM, and dc conductivity studies. FTIR spectra were deconvoluted to track the change in the fraction of the TeO4 and BO4 units. FTIR results showed a linear decrease in both fractions of the N4Te and N4B units with B2O3 content, while BO4 and BO3 units increased with nearly equal values up to 40 mol% B2O3. The rate of increasing BO3 was greater than BO4 units for glasses with > 40 mol% B2O3. Density linearly decreased, whereas molar volume increased when replacing TeO2 with B2O3. XRD and SEM revealed formation of AgTeO3 and AgBO3 micro-crystallites depending on the concentration of B2O3. The introduction of B2O3 into the Ag2O–TeO2 network caused an increase in the conductivity up to 50 mol%, which decreased for further additions of B2O3 content. Finally, the conductivity of the studied glasses was more strongly affected by the pre-exponential factor rather than the activation energy.