Five samples of ternary semiconducting 65V2O5 –xNiO–(35–x) TeO2 glasses, with 5 ≤ x ≤ 25 (x in mol%), were prepared using a press-quenching method from a glass melt. The thermoelectric Power (TEP), density, oxygen molar volume (Vm) and x-ray diffraction (XRD) were analyzed. TEP measurements were conducted within the temperature range of 300 – 506 K for the mentioned glass compositions. Information on the creation of polarons and the disorder energy arising from random fields was gathered. By applying Heikes’ equation and the small polaron model theory to the TEP, the results obtained from experimental data were effectively explained. The study revealed that an increase in the NiO content in the glass led to a rise in density and a consistent decrease in molar volume. All glasses exhibited a singular phase structure.