In this study, real-time and in-situ permittivity measurements under intense microwave electromagnetic fields are proposed as a powerful technique for the study of microwave-enhanced thermal processes in materials. In order to draw reliable conclusions about the temperatures at which transformations occur, we address how to accurately measure the bulk temperature of the samples under microwave irradiation. A new temperature calibration method merging data from four independent techniques is developed to obtain the bulk temperature as a function of the surface temperature in thermal processes under microwave conditions. Additionally, other analysis techniques such as Differential Thermal Analysis (DTA) or Raman spectroscopy are correlated to dielectric permittivity measurements and the temperatures of thermal transitions observed using each technique are compared. Our findings reveal that the combination of all these procedures could help prove the existence of specific non-thermal microwave effects in a scientifically meaningful way.