XRD, IR spectra, DTA, density, oxygen molar volume and dc conductivity of barium vanadate glasses of compositions xBaO-(100 - x)V2O5, where x = 30, 35, 40, 45 and 50 mol%, are reported. The IR studies of the glasses suggest the glass network is built up of mainly VO4 polyhedra. The glass transition temperatures are observed to increase with an increase of BaO content in the compositions. The cross-linking density decrease with increasing BaO content in the compositions. Introduction of BaO into the V2O5 matrix changes the 2D layer structure of the crystalline V2O5 into a more complicated 3D structure. Analysis of the electrical properties has been made in the light of small polaron hopping model. The parameters obtained from the fits of the experimental data to this model are reasonable and consistent with glass composition. The conduction is attributed to non-adiabatic hopping of small polaron. (c) 2005 Published by Elsevier B.V.