The influence of PbSO4 content on structure, optical and electrochemical properties of the 4PbO(2)center dot Pb glassy network was investigated using XRD, FTIR and UV-VIS spectroscopies, cyclic voltammetry measurements and optical gap energy calculations. FTIR data shows that the bending modes of the Pb-O-Pb and O-Pb-O linkages from [PbO4] structural units allow the intercalation of entities provided from sulfate ions in the host chain network. Further, the increase of PbSO4 content up to 15 mol% in the host matrix implies formation of PbSO3 and PbO2 crystalline phases. Significant decrease of the gap energy can be understood in the terms of structural changes that are taking place with the introduction of PbSO4 into the glassy and vitroceramic network. Cyclic voltammograms of the electrode glasses having the xPbSO(4) center dot (100 - x)[4PbO(2)center dot Pb] composition where x = 0-10 mol% PbSO4 show that the presence of PbSO4 in the host matrix can inhibit the growth of the anodic MO film and can ensure a better conductivity of the electrode in a rechargeable battery. Thus, the studied samples can be promising electrode candidates for rechargeable batteries. At higher PbSO4 content, up to 15 mol%, electrochemical performances of the electrode were inhibited due to the presence of PbSO3 crystalline phase in the host network. (C) 2015 Elsevier B.V. All rights reserved.