A self-assembled supramolecular bilayer (SAB) at the zinc (Zn) anode-electrolyte interface enables ordered planar plating/stripping of Zn, achieving a depth of discharge (DOD) exceeding 90% with negligible thickness fluctuation and long-term stable cycling. The SAB, formed by a lipopeptide with a hydrophobic aliphatic chain and a positively charged amino acid, creates in-plane Zn–N bonds, facilitating ordered Zn plating/stripping with a (0001)Zn orientation and minimal side reactions. This results in a high cumulative capacity of 11,000 mAh cm⁻², the highest reported for Zn-based batteries. The SAB significantly improves the electrochemical stability of Zn anodes by reducing side reactions, inhibiting dendrite formation, and enhancing the uniformity of Zn deposition. The ordered planar plating/stripping mechanism is supported by various analyses, including scanning electron microscopy (SEM), X-ray diffraction (XRD), and molecular dynamics simulations, which confirm the in-plane orientation and synchronized activation of Zn atoms. The SAB also enhances the transport of Zn²+ ions, leading to improved cycling stability and high Coulombic efficiency. The SAB-Zn anode was further integrated into full cells with MnO₂ and NiHCF cathodes, achieving high energy density and excellent cycle life. The study provides insights into the ordered plating/stripping of metal anodes for rechargeable energy-dense batteries.A self-assembled supramolecular bilayer (SAB) at the zinc (Zn) anode-electrolyte interface enables ordered planar plating/stripping of Zn, achieving a depth of discharge (DOD) exceeding 90% with negligible thickness fluctuation and long-term stable cycling. The SAB, formed by a lipopeptide with a hydrophobic aliphatic chain and a positively charged amino acid, creates in-plane Zn–N bonds, facilitating ordered Zn plating/stripping with a (0001)Zn orientation and minimal side reactions. This results in a high cumulative capacity of 11,000 mAh cm⁻², the highest reported for Zn-based batteries. The SAB significantly improves the electrochemical stability of Zn anodes by reducing side reactions, inhibiting dendrite formation, and enhancing the uniformity of Zn deposition. The ordered planar plating/stripping mechanism is supported by various analyses, including scanning electron microscopy (SEM), X-ray diffraction (XRD), and molecular dynamics simulations, which confirm the in-plane orientation and synchronized activation of Zn atoms. The SAB also enhances the transport of Zn²+ ions, leading to improved cycling stability and high Coulombic efficiency. The SAB-Zn anode was further integrated into full cells with MnO₂ and NiHCF cathodes, achieving high energy density and excellent cycle life. The study provides insights into the ordered plating/stripping of metal anodes for rechargeable energy-dense batteries.