The microwave absorption (MA) performance of carbon materials is severely hindered by their drawbacks of lacking magnetic loss ability and mismatched electromagnetic impedance. In this work, utilizing sustainable biomass kapok as a template, the hierarchically tubular C/Co nanoparticle composite is rationally constructed to acquire the enhanced MA performance for the first time. The fruit‐tree‐like hierarchical structure is composed from a “trunk” of kapok‐derived carbon microtubes, a “branch” of entangled carbon nanotubes, and “fruit” of Co nanoparticles embedded in the nanotubes. Such a hierarchically tubular structure offers the composite: i) a submillimeter‐scale 3D magnetic coupling network and reinforced magnetic loss ability, ii) a hierarchical dielectric carbon network, iii) better matched impedance, confirmed by the off‐axis electron holography and micromagnetic simulation. Accordingly, the as‐prepared hierarchically tubular carbon composite demonstrates impressive MA performance, with a maximum reflection loss of as much as −52.3 dB and a broad absorption bandwidth of 5.1 GHz. These encouraging achievements light the way to the development of the hierarchical microstructure of magnetic absorbents.

Core@shell structures have been attracting extensive attention to boost microwave absorption (MA) performance due to the unique interfacial polarization. However, it still remains a challenge to synthesize sophisticated 1D semiconductor‐based materials with excellent MA competence. Herein, a hierarchical cable‐like TiO2@Fe3O4@PPy is fabricated by a sequential process of solvothermal treatment and polymerization. The complex permittivity of ternary composites can be optimized by tunable PPy coating thickness to improve the loss ability. The maximum reflection loss can reach −61.8 dB with a thickness of 3.2 mm while the efficient absorption bandwidth can achieve over 6.0 GHz, which involves the X and Ku band at only a 2.2 mm thickness. Importantly, the heterojunction contacts constructed by PPy–Fe3O4 and Fe3O4–TiO2 contribute to the enhanced polarization loss. Besides, the configuration of magnetic Fe3O4 sandwiched between dielectric TiO2 and PPy facilitates the magnetic stray field to radiate into the TiO2 core and out of the PPy shell, which significantly promotes magnetic–dielectric synergy. Electron holography validates the distinct charge distribution and magnetic coupling. The new findings might shed light on novel structures for functional core@shell composites and the design of semiconductor‐based materials for microwave absorption.

Cabbage-like ZnCo2O4 with abundant flakes possess a maximum RL value of −36.33 dB and the effective bandwidth of 5.11 GHz.