The formation of a strong coordination structure, [Zn(H₂O)₆]²⁺ often increases direct contact between the solvated H₂O and Zn anodes on the inner Helmholtz layer, which exacerbates undesirable side reactions and dendrite growth, hindering the practical application of aqueous Zn metal batteries. Researchers identify that the solvated H₂O can be effectively minimized by an artificial solid electrolyte interphase (SEI) consisting of highly nitrogen-doped amorphous carbon (NC) and perfluorosulfonic acid polymer (Nafion). Theoretical and experimental analyses reveal that NC raises the Fermi level of the composite SEI and activates the non-coordinating charge transfer from the SEI to [Zn(H₂O)₆]²⁺, which leads to ultrafast desolvation of hydrated Zn-ions in the outer Helmholtz layer; while the Nafion framework ensures selective transport channels for Zn ions. Remarkably, the derived NC-Nafion@Zn symmetric cell exhibits a long lifespan (3400 h, 1 mA cm^-2; 2000 h, 5 mA cm^-2); moreover, the NC-Nafion@Zn//Mn₄O₃-carbon nanotubes full battery delivers ultralong cycling stability of 9300 cycles at 2 A g^-1 with a high retention of 91.3%.