In the present work, the experimental characterization of the pseudo-binary PbO-Bi2O3 cut has been performed by differential thermal analysis (DTA), isothermal annealing, powder X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), and electron probe microanalysis (EPMA). A thermodynamic assessment according to the Calphad method was also performed based on the present results as well as previous experimental data using the ThermoCalc software. (c) 2008 Elsevier Ltd. All rights reserved.