Aqueous zinc-ion batteries (AZIBs) are plagued by water-rich and unstable electrolyte/electrode interface, which results in poor reversibility and short lifespan. Herein, trace sodium perfluorononyloxybenzenesulfonate (OBS) and bismuth potassium citrate (BPC) additives collaboratively construct a zincophilic and water-shielding interface. Both OBS and BPC molecules preferentially adsorb on the Zn anode, forming a H₂O-blocking layer to suppress water-induced side reactions. Concurrently, upon cycling, OBS decomposes and forms ZnF₂ with high ionic conductivity, while Bi³⁺ derived from BPC is electrochemically reduced to metallic Bi⁰, serving as zincophilic nucleation sites. This in-situ formed ZnF₂/Bi-modified interface synergistically regulates Zn²⁺ flux and homogenizes the interfacial electric field. Consequently, the Zn||Zn symmetric cell achieves exceptional cycling stability over 6600 h at 1 mA·cm⁻² and 1 mAh·cm⁻², and a lifespan over 1000 h at high current density and areal capacity (3 mA·cm⁻² and 3 mAh·cm⁻²). The full cell paired with NH₄V₄O₁₀ cathode delivers a capacity retention of 95.54% after 500 cycles at 1 A·g⁻¹, substantially outperforming the baseline electrolyte. This streamlined strategy in-situ constructs a multifunctional hybrid interphase, paving a new way for durable and high-performance AZIBs.

The unstable zinc anode/electrolyte interface induced by corrosion, interfacial water splitting reaction, and dendrite growth seriously degrades the performances of metal Zn anode in aqueous electrolyte. Herein, the nucleation and growth of zinc hydroxide sulfate (ZHS), an interfacial by-product, has been tailored by Tween 80 in the electrolyte, which thereby assists in in-situ forming a dense solid electrolyte interphase (SEI) with small-sized ZHS and evenly distributed Tween 80. This SEI has high corrosion resistance and uniform distribution of zinc ions, which not only contributes to blocking the interfacial side reactions but also induces stable and calm zinc plating/stripping. Consequently, the modified electrolyte can confer the assembled Zn||Zn symmetric cell with a stable operation life over 1500 h at 1 mA·cm⁻² and 1 mAh·cm⁻² as well as the practical Zn||NH₄V₄O₁₀ full battery with a high-rate capacity of 120 mAh·g⁻¹ at the current density of 5 A·g⁻¹. This work provides a way for regulating and reusing interfacial by-products, and a new sight on stabilization electrodes/electrolyte interfaces.