An impedance-optimized hierarchical TiO 2 @Fe/C@TiO 2 vesicular carbon microtube is constructed for the first time via coaxial electrospinning and solvothermal method. Benefit from the integration of cavities, highly dispersed magnetic nanoparticles, and dielectric coating, the impedance is effectively improved by dielectric-magnetic synergy. The unique structure simultaneously fulfills a dual-network of micron-scale magnetic interaction and charge transfer, embedding the composite with enhanced magnetic and dielectric loss. The interfacial polarization and multiple reflections further promote microwave absorption. • 1D vesicular structure was successfully constructed via coaxial electrospinning. • Structural and compositional integration progressively improved impedance. • Strong magnetic-dielectric synergy of quaternary components in this absorber. • Electron holography confirmed magnetic coupling and charge transfer dual-network. Impedance matching ( Z ) is a key issue requested by high-efficient microwave absorption materials, which remains a major challenge. Lacking magnetic loss capacity and electromagnetic impedance balance, the microwave attenuation capacity of carbon-based absorbers urgently needs to be improved. Herein, a TiO 2 @Fe/C@TiO 2 vesicular carbon microtube was reasonably constructed by coaxial electrospinning. The characteristic impedance was gradually improved by introducing cavities, magnetic Fe particles and dielectric TiO 2 coating. The composite achieves an enhanced microwave performance with a maximum reflection loss of as strong as − 60.98 dB and a broad absorption bandwidth of 4.8 GHz at only 2.0 mm thickness. Such a well-integrated hierarchically vesicular carbon microtube with a tubular porous structure endows the assembly with high magnetic anisotropy and multiple interfaces, further offers the composites: i) the dual-networks of micron-scale 1D anisotropic magnetic coupling and charge conduction, ii) dielectric-magnetic synergy of quaternary components, iii) progressively matched impedance, proved by micromagnetic simulation and electron holography. This finding might have great significance in the impedance matching control of high-performance microwave absorbents.