The paper reports a breakthrough in the development of zinc (Zn) anodes for energy-dense batteries, addressing the issue of low utilization and irreversibility in "hostless" metal anodes. The authors introduce an ordered planar plating/stripping process for Zn anodes, which enables a depth of discharge (DOD) exceeding 90% with minimal thickness fluctuation and long-term stable cycling. This is achieved through the formation of a self-assembled supramolecular bilayer (SAB) at the Zn anode-electrolyte interface, which preferentially promotes (0001)Zn orientation during the charge/discharge process. Real-time tracking of Zn atom migration reveals that the ordered planar plating/stripping is driven by in-plane Zn-N bindings and a gradient energy landscape at the reaction fronts. The study provides insights into the ordered plating/stripping of metal anodes, offering a promising approach for rechargeable energy-dense batteries.The paper reports a breakthrough in the development of zinc (Zn) anodes for energy-dense batteries, addressing the issue of low utilization and irreversibility in "hostless" metal anodes. The authors introduce an ordered planar plating/stripping process for Zn anodes, which enables a depth of discharge (DOD) exceeding 90% with minimal thickness fluctuation and long-term stable cycling. This is achieved through the formation of a self-assembled supramolecular bilayer (SAB) at the Zn anode-electrolyte interface, which preferentially promotes (0001)Zn orientation during the charge/discharge process. Real-time tracking of Zn atom migration reveals that the ordered planar plating/stripping is driven by in-plane Zn-N bindings and a gradient energy landscape at the reaction fronts. The study provides insights into the ordered plating/stripping of metal anodes, offering a promising approach for rechargeable energy-dense batteries.