Two kinds of Fe/amorphous carbon (a-C) submicron fibers were prepared by electrospinning using polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN) as precursor polymer, followed by carbonization under the same conditions. Contributed to the different reaction mechanisms during the annealing process, different phases namely graphite carbon (g-C) and Fe4N formed at the interface between the Fe nanoparticles and the a-C matrix. Electromagnetic absorption properties have shown that the Fe@Fe4N submicron fibers have superior absorption performance than the Fe@g-C ones. The minimal reflection loss (RL) value of the former is - 39.8 dB at 5.4 GHz with the absorber thickness of 5.0 mm, and the effective absorption bandwidth (RL <= - 10 dB) can reach 5.0 GHz when the absorber thickness is 2.5 mm. By contrast, the Fe@g-C submicron fibers have little absorption. The attenuation constant, impedance matching coefficient, complex permittivity and complex permeability were investigated in detail. The microstructure and composition were explored various superior tools. The results revealed that the interface Fe4N has a critical role in affecting the magnetic loss and dielectric loss, which brings better impedance matching and relatively low dielectric loss. Therefore, the Fe@Fe4N submicron fibers have excellent microwave absorbing properties. [GRAPHICS] .