Microwave-assisted processes have recognized advantages over more conventional heating techniques. However, the effects on the materials’ microstructure are still a matter of study, due to the complexity of the interaction between microwaves and matter, especially at high temperatures. Recently developed advanced microwave instrumentation allows the study of high temperature microwave heating processes in a way that was not possible before. In this paper, different materials and thermal processes induced by microwaves have been studied through the in situ characterization of their dielectric properties with temperature. This knowledge is crucial in several aspects: to analyze the effects of the microwave field on the reaction pathways; to design and optimize microwave-assisted processes, and to predict the behavior of materials leading to repeatable and reliable heating processes, etc.