Highly symmetrical and streamlined nanostructures possessing unique electron scattering, electron‐phonon coupling, and electron confinement characteristics have attracted a lot of attention. However, the controllable synthesis of such a nanostructure with regulated shapes and sizes remains a huge challenge. In this work, a peanut‐like MnO@C structure, assembled by two core–shell nanosphere is developed via a facile hydrogen ion concentration regulation strategy. Off‐axis electron holography technique, charge reconstruction, and COMSOL Multiphysics simulation jointly reveal the unique electronic distribution and confirm its higher dielectric sensitive ability, which can be used as microwave absorption to deal with currently electromagnetic pollution. The results reveal that the peanut‐like core–shell MnO@C exhibits great wideband properties with effective absorption bandwidth of 6.6 GHz, covering 10.8–17.2 GHz band. Inspired by this structure‐induced sensitively dielectric behavior, promoting the development of symmetrical and streamlined nanostructure would be attractive for many other promising applications in the future, such as piezoelectric material and supercapacitor and electromagnetic shielding.