A system has been developed, based on the cavity perturbation technique, for measuring the complex scalar permittivity of materials at frequencies between 50 MHz and 3 CHz, and up to a temperature of 1400°C. Measurements have been made on several classes of materials, including metallic oxides, conventional and advanced ceramics, fabrics, earthenwares, geological and biological materials, foods, glasses, organics and ferrites. Some materials remain unchanged by thermal cycling, but many undergo irreversible changes; the latter are of interest in microwave processing. The system measures the complex dielectric constant of materials during conventional heating, curing or sintering. Correlating these microwave measurements with other diagnostic techniques will help in the understanding of these processes in several classes of materials.