Lithium antimony lead germanate glasses doped with different concentrations of Cr 2 O 3 (ranging from 0 to 0.5mol %) were synthesized. The optical absorption and ESR spectral studies have indicated that there is a gradual increase in presence of octahedral chromium ions with increase of Cr 2 O 3 concentration in the glass network. These studies have also revealed that a fraction of chromium ions get oxidized into Cr 5+ and Cr 6+ states. IR and Raman spectroscopic studies have pointed out that there is an increasing degree of depolymerization of the titled glass network with increase of Cr 2 O 3 content. The dielectric parameters (viz., dielectric constant, loss and electrical modulus coefficients measured over a wide range of frequency and temperature) and also ac conductivity were found to increase with increase of Cr 2 O 3 content. The reasons for such increase were discussed quantitatively in terms of various polarization mechanisms coupled with structural variations of the glass network.