The effects of V2O5 concentration on semiconducting xV2O5–(1-x) (0.25Nd2O3–0.75ZnO) glass nanocomposites were investigated by structural, optical, and electrical conductivity studies. The composition dependency of physical attributes like density, molar volume, bond dissociation energy, number of bonds per unit volume, etc., was established. Using X-ray diffraction and field-emission scanning electron microscopy, we identified the presence of different nanocrystallites and amorphousness. DC electrical conductivity was caused by the small polaron hopping due to the presence of V4+ and V5+ valence states, enhanced as the small polaron radius was reduced with rising V2O5 concentration. The non-overlapping small polaron tunnelling (NSPT) model was the preferred AC conduction process, and reducing nature of tunnelling distance enhanced AC conductivity with increasing V2O5 concentration. We modified the existing NSPT model to get reasonable values for fitting parameters. The scaled AC conductivity spectra revealed temperature independence and the composition-dependent conductivity relaxation process of small polarons.