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Two kinds of porous carbon and magnetic particles-based composite nanofibers (PCNTF-CoFe and PCNTF-NiFe) were synthesized for electromagnetic wave (EMW) absorption. Magnetic particles were used as the catalyst to increase the crystallinity of carbon and the corresponding dielectric loss ability, while porous structure was designed to improve the impedance matching. According to the results, the dielectric loss abilities of PCNTF-CoFe and PCNTF-NiFe are enhanced without significant degradation in their impedance matching condition. Therefore, through the polarization and conduction-induced dielectric loss together with the natural and exchange resonance-induced magnetic loss, the incident EMW can be attenuated rapidly inside PCNTF-CoFe and PCNTF-NiFe. PCNTF-CoFe shows a minimum reflection loss (RL min) of −54.6 dB and effective band width (RL≤-10 dB, EABW) of 6.0 GHz at 2.0 mm, while PCNTF-NiFe shows RL min of −33.4 dB and EABW of 5.7 GHz at 1.7 mm. Consequently, PCNTF-CoFe and PCNTF-NiFe can be promising candidates for application in EMW absorption. [Display omitted] • Two kinds of carbon nanofiber-based composites were designed for EMW absorption. • The conduction loss ability was enhanced due to a higher crystallinity of carbon. • CNTs were generated on carbon nanofiber under the catalyzation of MNPs. • PCNTF-CoFe and PCNTF-NiFe have a hierarchical structure. • PCNTF-CoFe and PCNTF-NiFe can be promising candidates for EMW absorption. [ABSTRACT FROM AUTHOR]