Carbon-based materials have been widely explored as electromagnetic (EM) wave absorbing materials with specific surface areas and low density. Herein, novel porous carbon/SiOC ceramic composites materials (porous C/sp-SiOC) were prepared from the binary mixture, which used the low cost pitch as carbon resource and the polysilylacetylene (PSA) as SiOC ceramic precursor. With the melt-blending-phase separation route, the PSA resin formed micro-spheres in the pitch. Then, numerous SiOC ceramic micro-spheres were generated in porous carbon matrices during the pyrolysis process. By changing the percent of SiOC, the microstructure and wave absorption of porous C/sp-SiOC composites could be adjusted. The synergistic effect of the unique structure, the strong interfacial polarization, and the optimized impedance matching properties contributed to the excellent absorption performance of porous C/sp-SiOC composites. The minimum reflection loss for porous C/sp-SiOC absorber reached -56.85 dB, and the widest effective bandwidth was more than 4 GHz with a thickness of only 1.39 mm. This presented research provides an innovative and practical approach to developing high-performance porous carbon-based microwave absorption materials from green chemistry.