Although aqueous zinc-ion batteries (AZIBs) show immense promise for large-scale energy storage, their commercialization is critically hindered by water-induced parasitic reactions and uncontrolled zinc dendrite proliferation. Inspired by the “regulation–transport–capture” interfacial homeostasis mechanism of the cellular glycocalyx, we engineer a biomimetic hierarchical heterogeneous interface (Sb-MXene(PMETAC)). Within this interface, poly([2-(methacryloyloxy)ethyl]trimethylammonium chloride) (PMETAC) utilizes its high-density quaternary ammonium groups to convert solvated water into bound water, suppressing side reactions and promoting Zn2+ desolvation. Simultaneously, the MXene framework restricts bulky anions and regulates ion flux, while the underlying Sb layer acts as a zincophilic template to guide horizontal epitaxial growth. Owing to this synergistic effect, the modified symmetric battery sustains exceptional cycling stability and an ultra-long cycle life exceeding 5000 h at 2 mA cm−2 and 1 mA h cm−2 (50 times longer than that of bare zinc). Coupled with an AlVO-NMP cathode, the full battery exhibits a high capacity retention rate of 71.7% after 5000 cycles at a high rate of 5 A g−1. This work provides a biomimetic interface design concept for dual thermodynamic–kinetic synergistic regulation of interfaces in high-performance aqueous metal batteries.