Understanding Bonding Nature of α‐Keggin Polyoxometalates [XW₁₂O₄₀]ⁿ⁻ (X = Al, Si, P, S): A Generalized Superatomic Perspective

α‐Keggin polyoxometalates (POMs) [XW₁₂O₄₀]ⁿ⁻ (X = Al, Si, P, S) are widely used in batteries owing to their remarkable redox activity. However, the mechanism underlying the applications appears inconsistent with the widely accepted covalent bonding nature. Here, first‐principles calculations show that XW₁₂ are core–shell structures composed of a shell and an XO₄ⁿ⁻ core, both are stabilized by covalent interactions. Interestingly, owing to the presence of a substantial number of electrons in W₁₂O₃₆ shell, the frontier molecular orbitals of XW₁₂ are not only strongly delocalized but also exhibit superatomic properties with high‐angular momentum electrons that do not conform to the Jellium model. Detailed analysis indicates that energetically high lying filled molecular orbitals (MOs) have reached unusually high‐angular momentum characterized by quantum number K or higher, allowing for the accommodation of numerous electrons. This attribute confers strong electron acceptor ability and redox activity to XW₁₂. Moreover, electrons added to XW₁₂ still occupy the K orbitals and will not cause rearrangement of the MOs, thereby maintaining the stability of these structures. Our findings highlight the structure–activity relationship and provide a direction for tailor‐made POMs with specific properties at atomic level.