A novel high-temperature resistant calcium aluminate cement-based electromagnetic wave absorption composites were prepared using carbon fibers, Al2O3 hollow spheres, and expanded polystyrene spheres (EPS). EPS, as a pore forming agent, was oxidized as to form pores at high temperatures. The effects of carbon fibers doping levels and various high-temperature treatment on the permittivity of the composites from 0.3-18 GHz were investigated in detail. Additionally, a high-temperature resistant porous cone cement-based electromagnetic wave absorption structure was designed, and its microwave absorption mechanism was explored. The findings indicated that the permittivity of electromagnetic wave absorption composites exhibited stability even after undergoing high-temperature treatments below 350°C, while experiencing a decrease at 500°C. Following cyclic treatments at temperatures of 200°C and 350°C, the cone calcium aluminate porous cement-based composites still exhibited outstanding electromagnetic wave absorption performance, achieving reflection loss (RL) bandwidths below -30 dB of 17.4 GHz and 17.2 GHz, respectively, within the frequency range of 0.3-18 GHz. Furthermore, the RL of the composite from 4-18 GHz after 500°C treatment remained less than -50 dB. Thus, present work associated with the materials and structural design of calcium aluminate porous cone cement-based composites provided a potential insight into the high-temperature electromagnetic wave absorption engineering applications.