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Constructing the adjustable surface conductive networks is an innovation that can achieve a balance between enhanced attenuation and impedance mismatch according to the microwave absorption mechanism. However, the traditional design strategies remain significant challenges in terms of rational selection and controlled growth of conductive components. Herein, a hierarchical construction strategy and quantitative construction technique are employed to introduce conductive metal–organic frameworks (MOFs) derivatives in the classic yolk–shell structure composed of electromagnetic components and the cavity for remarkable optimized performance. Specifically, the surface conductive networks obtained by carbonized ZIF‐67 quantitative construction, together with the Fe₃O₄ magnetic core and dielectric carbon layer linked by the cavity, achieve the cooperative enhancement of impedance matching …