Metal–organic framework (MOF)-derived composites have gained wide attention due to their specific structures and enhanced performance. In this work, we prepared carbon nanotubes with Fe nanoparticles connected to two-dimensional (2D) hierarchical carbon network composites via a low-pressure gas–solid reaction strategy. Specifically, the three-dimensional (3D) networks derived from ZIF-8 exploited the carbon nanotubes with the function of charge modulation. Meanwhile, we utilized the interconnected 2D nanostructures to optimize impedance matching and facilitate multiple scattering, ultimately improving the overall microwave absorption performance. Furthermore, based on the well-designed structures, the composites prepared at 800 °C (Fe-N-C@CNTs-800) achieved the best reflection loss (RL) of −58.5 dB, thereby obtaining superior microwave absorption performance. Overall, this study provides a good groundwork for further investigation into the modification and dimension design of novel hierarchical microwave absorbers.