Waelz-oxide is a raw material for the production of metallic zinc. Waelz-oxide contains impurities of zinc and lead chlorides and fluorides. Halides have a negative effect on the process of zinc electrolysis. Halides have a relatively low boiling point; therefore, they are removed into the gas phase by calcining Waelz-oxide at 800–850 °С. To intensify the process, calcination is sometimes carried out at elevated temperatures of 1100–1250 °С. However, an increase in temperature leads to partial melting and granulation of the calcined product. In the present work, the chemical and phase composition of the initial and calcined Waelz-oxide was studied. Thermodynamic modeling of phase and chemical transformations of Waelz-oxide components during heating has been performed. Experiments on calcination of Waelz-oxide in laboratory conditions at temperatures of 600–1250 °C were carried out. It was found that partial melting and granulation of Waelz-oxide is the result of the formation of fusible eutectics containing lead oxide. Lead oxide is formed as a result of decomposition of lead sulfate when heated above 1100 °C. A similar effect is not observed at a standard calcination temperature of 850 °C.