Spatially Decoupled Charge Compensation Enables Versatile Cation–Anion Co‐Intercalation in Layered Metal Oxide Cathodes

ABSTRACT Multivalent cation–anion co‐(de)intercalation offers a promising pathway to higher energy densities in multivalent ion batteries. However, its practical realization is challenged by lattice strain and the lack of effective dual charge‐compensation strategies. Here, we report a layered vanadium oxide cathode with pre‐intercalated melamine ligands (MeVO) that enables a spatially decoupled charge‐compensation mechanism—organic ligands serve as redox centers for anions, while metal sites accommodate multivalent cation redox. This design alleviates electrostatic crowding, promotes ion mobility, and preserves structural integrity. Using Mg 2 + ‐TFSI − as a representative system, MeVO delivers a record cycle life of over 36 000 cycles at a loading of approximately 3 mg cm − 2 and an areal capacity of 3.3 mAh cm − 2 at a higher loading of 16.4 mg cm − 2 , surpassing leading Mg‐ion cathodes. The hybrid structure also supports co‐(de)intercalation of various multivalent cations and anions, demonstrating its potential as a versatile intercalation platform for high‐performance energy storage.