Defect modulation strategies have been shown to be an effective way to design efficient EMW absorbing materials, but the coexistence of multiple loss mechanisms due to the complexity of the existing models makes it difficult to elucidate the mechanism by which defect-induced dielectric losses dominate. In this work, p(C3O2)x is applied for the first time in the field of EMW absorption and the concentration of defects in the sample is controlled by changing the pyrolysis temperature. In addition, the unique molecular structure of p(C3O2)x enables the prepared samples to completely eliminate the interference of interfacial polarization and magnetic loss on EMW dissipation. The results show that the dielectric loss induced by defects significantly enhances the EMW absorption performance as the concentration of defects increases, but excessive defects lead to a sudden drop in the conductivity of the sample and reduce the EMW absorption performance. In which, the RLmin of OC-800 can reach −51.0 dB, and the EAB of OC-900 can go up to 5.6 GHz at only 1.6 mm. Finally, CST simulation verified the potential application of the prepared absorber in real scenarios. This work has improved the theoretical basis of the effect of defect-induced dielectric loss on EMW absorbing properties, and the simple synthetic raw materials and routes have made the industrialized production of highly efficient EMW absorbing materials possible.