Glasses and vitroceramics in the xMoO(3)center dot(100 - x)[4PbO(2)center dot Pb] system with x = 5-50 mol%MoO3 were prepared by melt quenching method. The influence of MoO3 content on optical properties and structure of the 4PbO(2)center dot Pb host network was investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), Raman, photofluorescence and X-ray photoelectron (XPS) spectroscopies. The X-ray patterns show the presence of a small amount of Pb2MoO5 crystalline phase in the sample with x = 40 mol%MoO3. By increasing of MoO3 content up to 50 mol% MoO3, Pb2MoO5 and tetragonal PbO crystalline phases were detected. Raman data show the bending modes of the O-Pb-O linkages which allow the intercalation of [PbO4] structural units, isolated [MoO4] and deformed [MoO6] structural units as basic structural units formed by lead and molybdenum atoms. The photofluorescence spectroscopy data shows the transitions of Mo+5 and Pb2+ ions. According to the XPS data, the vitroceramic network contains mainly [MoO4] tetrahedral units and small amounts of [MoO6] octahedral units. (C) 2016 Elsevier B.V. All rights reserved.