Microwave heating is an intriguing method for the synthesis of inorganic solids offering a variety of advantages over conventional furnace heating, such as fast heating and cooling rates as well as volumetric and selective heating of precursors. However, there are many open questions regarding this “black‐box” process, and insights into the effect of microwave radiation on different types of solids are generally missing. In situ Raman spectroscopy is a powerful technique to unravel chemical transformations and identify intermediate species during microwave solid‐state syntheses. A major challenge is the temperature measurement under microwave conditions because (metallic) thermocouples cannot be used and optical pyrometry has significant drawbacks. In contrast, Raman thermometry is a viable method that relies on the temperature‐induced shift of Raman signals. Here, we use this method to estimate the temperature during microwave heating of a model system (titania) that undergoes a phase transition at temperatures >800°C. The estimation is derived from a flexible double exponential calibration function applied to Raman spectroscopic peak shifts in the temperature‐resolved furnace heating data, which was found to describe two titania modes (one anatase and one rutile) extremely well. Based on a detailed error and uncertainty analysis, we suggest options to further optimize Raman thermometry for use in high‐temperature microwave heating conditions.