Layered vanadium-based compounds are promising cathode materials for aqueous zinc ion batteries (ZIBs) due to their multi-electron reactions and adjustable ion-diffusion channels. However, the narrow interplanar spacing, strong binding with Zn2+, and vanadium dissolution significantly limit their further application. Herein, we present a defective (NH4)0.78V4O10-x·1.49H2O (N2) with a strong hydrogen bond as the cathode for ZIBs. Both experimental data and DFT calculation confirm that the triple effect of intercalating H2O, increasing oxygen defects, and introducing ammonium vacancy not only enriches the active sites but also restricts the NH4+ and vanadium by strong hydrogen bonds. Meantime, the electrostatic interaction between Zn2+ and framework is also improved, both in O-free and O-defect [VOn] polyhedrons. As expected, the N2 delivers a specific capacity of 533.1 mAh g−1 (398.2 Wh kg−1 at 184.4 Wh kg−1) at 0.5 C, a rate-capability of 225.4 mAh g−1 at 20 C, and without obvious capacity decay at 20 C over 2000 cycles.