Zn and Cl have been found in deposits in municipal solid waste (MSW) boilers and industrial boilers. This leads to the general belief that ZnCl 2 may play a role in corrosion of heat-transfer tubes, owing to its low melting temperature and high corrosivity. In this study, the thermal stability of the compounds ZnCl2, ZnSO4, and ZnO as well as mixtures of ZnCl2 and NaCl/KCl was investigated by means of thermogravimetric analysis/differential scanning calorimetry (TGA/DSC). The reactions of the Zn compounds with SO2/SO3 and HCl were also investigated. The results obtained show that ZnCl2 melts at 320 C. Above 400 C, ZnCl2 vaporizes and is partly oxidized to ZnO. ZnSO4 is stable up to 680 C, at which it decomposes and, subsequently, forms ZnO above 900 C. ZnO is stable at a much higher temperatures but can be chlorinated to ZnCl2 in the presence of HCl at temperatures around 300 C. In the presence of a large amount of NaCl/KCl, which is typically the case in actual boilers, ZnCl2 reacts with NaCl/KCl to form 2NaCl·ZnCl2 and 2KCl·ZnCl2, respectively. These compounds melt at temperatures lower than NaCl and KCl but higher than ZnCl2. The findings show the significance of understanding the thermal stability of various zinc compounds, how they interact with one another, and whether they react with alkali chlorides and other compounds in the deposits to assess the role of Zn in deposit formation and corrosion in boilers burning Zn-containing fuels.