Aqueous zinc-vanadium batteries (AZVBs) are severely limited by interfacial water-induced failure mechanisms, where uncontrolled water activity simultaneously triggers zinc dendrite growth at the anode and vanadium dissolution at the cathode. Existing strategies predominantly focus on stabilizing a single electrode interface, while the synchronized regulation of dual-electrode interfacial chemistry remains fundamentally challenging. Here, we report an amphiphilic molecular engineering strategy that enables interfacial water redistribution across both electrode interfaces using terpineol (TER) as a bifunctional electrolyte regulator. Owing to its hydrophilic-hydrophobic architecture, TER spontaneously constructs a self-assembled interfacial layer that simultaneously reconstructs Zn²⁺ solvation environments, disrupts hydrogen-bonded water networks, and repels reactive interfacial water from both zinc and vanadium surfaces. This dual-interface regulation homogenizes Zn²⁺ flux, suppresses hydrogen evolution and dendrite propagation, while concurrently inhibiting hydration-driven vanadium dissolution and cathode structural degradation. Consequently, the TER-regulated system achieves highly reversible Zn plating/stripping for over 4000 h at 1 mA·cm⁻² and enables Zn||NH₄V₄O₁₀ (NVO) full cells with 99.65% capacity retention after 800 cycles at 5 A·g⁻¹. More importantly, this work establishes an amphiphilic interfacial water regulation paradigm that synchronizes anode and cathode stabilization through one-molecule chemistry, offering a generalizable route toward durable aqueous multielectrode energy-storage systems.

Traditional aqueous electrolyte systems in zinc-ion batteries (ZIBs) often face challenges such as sluggish ion transfer kinetics, dendrite formation, and sudden battery failures in harsh temperature environments. Herein, we introduce a pioneering approach by integrating a bifunctional additive composed of ethylene glycol (EG) and sodium gluconate (Ga) into ZnSO₄ (ZSO) electrolyte to overcome these obstacles. The polyhydroxy structures of EG and Ga can reconstruct the hydrogen bond network of H₂O to improve its liquid stability, and also adjust the coordination environment around hydrated Zn²⁺. Additionally, Ga in the H₂O–EG mixture leads to the formation of a robust protective layer that promotes uniform deposition of Zn²⁺ ions and minimizes unwanted side reactions. Therefore, Zn anodes with 40% ZSO–Ga electrolyte can cycle for more than 3,000 h at 25 °C and 800 h at 50 °C. Furthermore, Zn||NH₄V₄O₁₀ (NVO) full batteries demonstrate remarkable cycle stability, lasting up to 10,000 cycles at 1 A g⁻¹ with a capacity retention of 79.1%. The multifunctional electrolyte additive employed in this study emerges as a promising candidate for enabling highly stable zinc anodes under diverse temperature conditions.