Herein, we present the structural evolution of polymer-derived SiOC ceramics with the pyrolysis temperature and the corresponding change in their microwave dielectric properties. The structure of the SiOC ceramics pyrolyzed at a temperature lower than 1200 °C is amorphous, and the corresponding microwave complex permittivity is pretty low; thus, the ceramics exhibit wave transmission properties. The Structural arrangement of free carbon in the SiOC ceramics mainly happens in the temperature range of 1200 °C-1300 °C due to the separation from the Si–O–C network and graphitization, while the structural arrangement of the Si-based matrix mainly occurs in the range of 1300 °C-1400 °C owing to the separation of SiC4 from the Si–O–C network to form nanocrystalline SiC. In pyrolysis temperature range of 1200 °C-1400 °C, the microwave permittivity of SiOC shows negligible change. At a pyrolysis temperature exceeding 1400 °C, the carbothermal reaction of free carbon and the Si–O backbone becomes significant, leading to the formation of crystalline SiC. The as-formed SiC and residual defective carbon improve the polarization loss of SiOC ceramics. In this case, the SiOC ceramics show significantly increased complex permittivity, exhibiting electromagnetic absorption characteristics. These characteristics promote the application of polymer-derived SiOC ceramics to high-temperature electromagnetic absorption materials.