The intercalation of n -butylamine into layer-structured α -ZrP benefits the formation of a dense layer, reduces the transfer barrier of Zn ²⁺ and increases the local concentration of Zn ²⁺ , leading to enhanced electrochemical performances for Zn anodes.

Driven by safety issues, environmental concerns, and high costs, rechargeable aqueous zinc‐ion batteries (ZIBs) have received increasing attention in recent years owing to their unique advantages. However, the sluggish kinetics of divalent charge Zn²⁺ in the cathode materials caused by the strong electrostatic interaction and their unsatisfactory cycle life hinder the development of ZIBs. Herein, organic cations and Zn²⁺ ions co‐pre‐inserted vanadium oxide ([N(CH₃)₄]_0.77,Zn_0.23)V₈O₂₀·3.8H₂O are reported as the cathode for ultra‐stable aqueous ZIBs, in which the weaker electrostatic interactions between Zn²⁺ and organic ion‐pinned vanadium oxide can induce the high reversibility of Zn²⁺ insertion and extraction, thereby improving the cycle life. It is demonstrated that ([N(CH₃)₄]_0.77,Zn_0.23)V₈O₂₀·3.8H₂O cathodes deliver a discharge capacity of 181 mA h g⁻¹ at 8 A g⁻¹ and ultra‐long life span (99.5% capacity retention after 2000 cycles). A reversible Zn²⁺/H⁺ ions (de)intercalation storage process and pseudocapacitive charge storage are characterized. The weaker interactions between organic ion and Zn²⁺ open a novel avenue for the design of highly reversible cathode materials with long‐term cycling stability.