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.