The dielectric properties of goethite and, in particular, the changes during the topotactic conversion of goethite to hematite were studied from room temperature to about 800 °C in the frequency range of 400 to 3000 MHz using the cavity perturbation technique. The complex permittivity, that is, both the real and the imaginary or absorptive parts (έ and ἕ), were measured under various heating regimens. In addition, thermogravimetric analysis (TGA) was performed to characterize the transformation of goethite to hematite. The Debye relaxation formalism was applied to the processes occurring both during and after the main dehydroxylation reaction to calculate the relaxation times. The Arrhenius equation for thermally activated relaxation times was used to determine the activation energies. Both the real and the absorptive parts of the permittivity exhibited a significant peak during the main part of the goethite to hematite decomposition reaction. Above the transformation, there was another, less dramatic, thermally activated increase in the permittivity values. The increase in the permittivities during the goethite to hematite transformation was attributed to the formation of quasi-free migrating radicals, for example, hydroxyl ions, oxygen ions, or hydrogen atoms, during the dehydroxylation of goethite. The derivative thermogravimetric analysis (DTGA) curve was found to be directly related to the transient values of the real and the imaginary permittivities. Higher heating rates resulted in an accelerated rate of dehydroxylation and therefore higher values of the transient permittivities. In the temperature range of 400 °C to 500 °C (i.e., just above the dehydroxylation peak), the real permittivity exhibited a varying frequency dependence, which suggested that changes were occurring in the newly formed, highly defected hematite structure, which is referred to as hydrohematite. During the reaction there were multiple relaxation processes and thus the Debye relationship could not be applied. However, at temperatures above about 500 °C, the structure stabilized, the Debye relationship was more closely followed, and the relaxation times could be determined as a function of temperature. The activation energy for the relaxation process above 500 °C was determined to be 0.47 kJ/mol.