Currently, heterogenous interface engineering on absorbers is shown to boost the electromagnetic wave absorption (EMA) performance effectively. However, challenges remain in investigating the mechanisms by studying heterojunctions between heterogeneous interfaces. Herein, a self-assembly Ti3C2Tx MXene/ZnCo2O4@ZnO (MZCZ) heterostructure with abundant Schottky heterogenous interfaces generating a controllable built-interface electric field (BIEF) effect is fabricated to achieve exceptional EMA ability. The formative BIEF between the unbalanced distribution charges promotes charge separation and migration, increasing polarization loss. Fortunately, the obtained MZCZ1 exhibits the reflection loss (RL) value of −69.78 dB under the ultralow thickness of 1.501 mm and the optimal minimum RL (RLmin) value of −74.41 dB, respectively. The excellent performance can be ascribed to the multiple polarization loss, conduction loss, natural resonance, and exchange resonance characteristics. Moreover, by the Computer Simulation Technology (CST) software, the designed circular cone and circular truncated cone periodicity structure with the MZCZ1 absorber both exhibit a super-wide effective absorption bandwidth (EAB) covering the whole C, X, and Ku band. This study can pioneer a novel approach to developing functional EMA materials and provide a valuable direction for further study of EMA mechanisms at heterogeneous interfaces.