Abstract Dual atoms (DAs), characterized by flexible structural tunability and high atomic utilization, hold significant promise for atom‐level coordination engineering. However, the rational design with high‐density heterogeneous DAs pairs to promote electromagnetic wave (EMW) absorption performance remains a challenge. In this study, high‐density Ni─Cu pairs coupled DAs absorbers are precisely constructed on a nitrogen‐rich carbon substrate, achieving an impressive metal loading amount of 4.74 wt.%, enabling a huge enhancement of the effective absorption bandwidth (EAB) of EMW from 0 to 7.8 GHz. Furthermore, the minimum reflection loss (RL min ) is −70.96 dB at a matching thickness of 3.60 mm, corresponding to an absorption of >99.99% of the incident energy. Both experimental results and theoretical calculations indicate that the synergistic effect of coupled Ni─Cu pairs DAs sites results in the transfer of electron‐rich sites from the initial N sites to the Cu sites, which induces a strong asymmetric polarization loss by this redistribution of local charge and significantly improves the EMW absorption performance. This work not only provides a strategy for the preparation of high‐density DA pairs but also demonstrates the role of coupled DA pairs in precisely tuning coordination symmetry at the atomic level.