Ceramizable (ceramifiable) silicone rubber-based composites are commonly used for cable insulation. These materials are able to create a protective ceramic layer during fire due to the ceramization process, which occurs at high temperature. When the temperature is increased, the polymer matrix is degraded and filler particles stick together by the fluxing agent, producing a solid, continuous ceramic phase that protects the copper wire from heat and mechanical stress. Despite increasing interest in these materials that has resulted in growing applications in the cable industry, their thermal behavior and ceramization process are still insufficiently described in the literature. In this paper, the thermal behavior of ceramizable silicone rubber-based composites is studied using microcalorimetry and Fourier transform infrared spectroscopy. The analysis of the experimental data made it possible to develop complete information on the mechanism of composite ceramization.