Knowledge of the high-temperature properties of ternesite (Ca5(SiO4)2SO4) is becoming increasingly interesting for industry in different ways. On the one hand, the high-temperature product has recently been observed to have cementitious properties. Therefore, its formation and hydration characteristics have become an important field of research in the cement industry. On the other hand, it forms as sinter deposits in industrial kilns, where it can create serious problems during kiln operation. Here, we present two highlights of in situ Raman spectroscopic experiments that were designed to study the high-temperature stability of ternesite. First, the spectra of a natural ternesite crystal were recorded from 25 to 1230 °C, which revealed a phase transformation of ternesite to the high-temperature polymorph of dicalcium silicate (α’L-Ca2SiO4), while the sulfur is degassed. With a heating rate of 10 °C/h, the transformation started at about 730 °C and was completed at 1120 °C. Using in situ hyperspectral Raman imaging with a micrometer-scale spatial resolution, we were able to monitor the solid-state reactions and, in particular, the formation properties of ternesite in the model system CaO-SiO2-CaSO4. In these multi-phase experiments, ternesite was found to be stable between 930 to 1020–1100 °C. Both ternesite and α’L-Ca2SiO4 were found to co-exist at high temperatures. Furthermore, the results of the experiments indicate that whether or not ternesite or dicalcium silicate crystallizes during quenching to room temperature depends on the reaction progress and possibly on the gas fugacity and composition in the furnace.