Glasses in the system xV2O5·20Li2O·(80−x) [0.6B2O3:0.4ZnO] (where 10≤x≤50) have been prepared by a simple microwave method. Microwave synthesis of materials offers advantages of efficient transformation of energy throughout the volume in an effectively short time. Conductivity in these glasses was controlled by the concentration of transition metal ion (TMI). The dc conductivity follows Arrhenius law and the activation energies determined by regression analysis varies with the content of V2O5 in a non-linear passion. This non-linearity is due to different conduction mechanisms operating in the investigated glasses. Impedance and electron paramagnetic resonance (EPR) spectroscopic studies were performed to elucidate the nature of conduction mechanism. Cole–cole plots of the investigated glasses consist of (i) single semicircle with a low frequency spur, (ii) two depressed semicircles and (iii) single semicircle without spur, which suggests the operation of two conduction mechanisms. EPR spectra reveal the existence of electronic conduction between aliovalent vanadium sites. Further, in highly modified (10V2O5mol%) glasses Li+ ion migration dominates.