The vaporization of individual lead and vanadium oxides and a wide range of compositions of PbO-V₂O₅ melts has been studied. The thermodynamic characteristics of the PbO-V₂O₅ system have been determined, PbO-V₂O₅ melts show negative deviations from the ideal behavior because of the formation of thermally stable compounds in their condensed phase. For gaseous lead vanadate PbV₂O ₆, the thermodynamic functions have been calculated and the standard enthalpies of formation and atomization have been determined.