This investigation consists of results of the studies on dielectric properties and a.c. conductivity of Li 2 O-Ga 2 O 3 -SiO 2 (LGS) glass with 2.0 mol% of Cr 2 O 3 , MoO 3 , WO 3 across 0.01 Hz to 1 MHz and 20 °C to 240 °C. Structural analysis using optical absorption and IR spectra indicated dopant ions predominantly in Cr 3+ , Mo 6+ /Mo 5+ , W 6+ states, and occupied T d and O h positions. Dielectric constant and conductivity were found to be the maximal for LGSMo glass, with the lowest impedance, while LGSCr glass exhibited the opposite trend. From the analysis of dipolar relaxation effects probable dipoles were identified in each glass. Studies on conductivity revealed that contribution of ionic components is very low and a substantial polaronic contribution in LGSMo glass, whereas, LGSCr glass showed a larger ionic component, specifically Li + ion diffusion and hence more useful material for solid-state batteries with respect to the other two glasses.