Ingenious microstructure design and suitable component regulation are the prevailing methods to meet the requirements of lightweight, broadband, and high-efficiency electromagnetic absorbing materials. Herein, petal-like magnetic Ni nanosheets on porous carbon nanofibers (Ni-PCF) are synthesized by electro-blown spinning, hydrothermal reaction, and high-temperature calcination. The construction of a porous carbon fiber skeleton originated from the in situ composition of the pore-forming agent (polystyrene (PS)), and the formation of petallike magnetic Ni nanosheets was derived from self-assembling during a hydrothermal reaction. The porous carbon fiber skeleton and petal-like Ni nanosheets could not only generate multiple reflections to extend the transmission pathway but also induce a synergistic effect of magnetic loss and dielectric loss to promote impedance matching, giving rise to more electromagnetic wave attenuation and energy dissipation. The good impedance matching, multiple reflections, and synergetic electric/magnetic losses originating from ingenious microstructures and suitable multicomponents resulted in the best microwave absorption performance of Ni-PCF 2 with a minimum reflection loss (RL min ) value of 37.93 dB at 6.08 GHz and an effective absorption bandwidth (EAB) of 4.43 GHz.