Precise and accurate temperature control is pertinent to studying thermally activated processes in thin films. Here, we present a calibration method for the substrate–film interface temperature using spectroscopic ellipsometry. The method is adapted from temperature calibration methods that are well developed for thermogravimetric analysis and differential scanning calorimetry instruments, and is based on probing a transition temperature. Indium, lead, and zinc could be spread on a substrate, and the phase transition of these metals could be detected by a change in the C signal of the ellipsometer. For water, the phase transition could be detected by a loss of signal intensity as a result of light scattering by the ice crystals. The combined approach allowed for construction of a linear calibration curve with an accuracy of 1.3 C or lower over the full temperature range.