Customizing Heterointerfaces in Multilevel Hollow Architecture Constructed by Magnetic Spindle Arrays Using the Polymerizing‐Etching Strategy for Boosting Microwave Absorption

Heterointerface engineering is evolving as an effective approach to tune electromagnetic functional materials, but the mechanisms of heterointerfaces on microwave absorption (MA) remain unclear. In this work, abundant electromagnetic heterointerfaces are customized in multilevel hollow architecture via a one‐step synergistic polymerizing‐etching strategy. Fe/Fe(3)O(4)@C spindle‐on‐tube structures are transformed from FeOOH@polydopamine precursors by a controllable reduction process. The impressive electromagnetic heterostructures are realized on the Fe/Fe(3)O(4)@C hollow spindle arrays and induce strong interfacial polarization. The highly dispersive Fe/Fe(3)O(4) nanoparticles within spindles build multi‐dimension magnetic networks, which enhance the interaction with incident microwaves and reinforce magnetic loss capacity. Moreover, the hierarchically hollow structure and electromagnetic synergistic components are conducive to the impedance matching between absorbing materials and air medium. Furthermore, the mechanisms of electromagnetic heterointerfaces on the MA are systematically investigated. Accordingly, the as‐prepared hierarchical Fe/Fe(3)O(4)@C microtubes exhibit remarkable MA performance with a maximum refection loss of −55.4 dB and an absorption bandwidth of 4.2 GHz. Therefore, in this study, the authors not only demonstrate a synergistic strategy to design multilevel hollow architecture, but also provide a fundamental guide in heterointerface engineering of highly efficient electromagnetic functional materials.