<p>Glasses with compositions <i>x</i>V₂O₅-(0.3−<i>x</i>)MoO₃-0.2ZnO-0.5TeO₂ (<i>x</i> = 0.05, 0.10, 0.15, 0.20) are synthesized using the Melt quenching method. The x-ray diffraction (XRD) pattern confirmed the amorphous character of the samples. With increasing amounts of dopant addition, the measured density rises from 4.35&#xa0;g&#xa0;cm⁻³ to 4.72&#xa0;g&#xa0;cm⁻³, followed by a reduction in molar volume from 35.74 cm³ to 34.17 cm³. Ultrasonic velocities obtained using the pulse-echo technique have been employed to evaluate the elastic moduli, Poisson’s ratio, and hardness. The observed longitudinal modulus increases from 53.59 GPa to 74.76 GPa, the bulk modulus increases from 29.72 GPa to 41.55 GPa, and Young’s modulus increases from 45.79 GPa to 62.38 GPa. In addition, the bond compression model is implemented to theoretically interpret the mechanical parameters of the studied glass samples. Furthermore, the differential scanning calorimetry (DSC) analysis shows an increase in both the glass transition temperature (<i>T</i>_<i>g</i>) (from 327°C to 341°C), and crystallization temperature (from 432°C to 452°C) with the inclusion of vanadium ions. The measurements of electrical conductivity reveal the thermally activated semiconducting properties, which exhibit well-defined direct-current (DC) and alternating-current (AC) regions following the Jonscher universal power law and Almond–West formalism. The significant decrease in DC, AC, and crossover activation energies with addition of vanadium clearly supports the assisted small polaron hopping process in the mixed-valence V⁴⁺/V⁵⁺ and Mo⁵⁺/Mo⁶⁺ centers. The integrated structural, mechanical, thermal, and electrical properties demonstrate V₂O₅ as an efficient multifunctional modifier, making the investigated glasses promising candidates for thermally stable, mechanically durable, and electrically active components in solid-state energy and electronic devices.</p>