Achieving stable Zn-ion batteries operating under high charging–discharging rates and a high depth of discharge (DOD) remains challenging due to intensified dendrite growth and side reaction. This work introduces a novel hygroscopic vanadium metal–organic framework (V-MOF) as a multifunctional protective layer to achieve an outstanding Zn anode. The as-fabricated battery can remain stable and high performance with high DOD of 85.5% and fast discharging rate of 50 mAh/cm². The hygroscopic V-MOF nature removes solvated shells and captures water as bonded/iced water within its structure, significantly suppressing side reactions. In addition, the V-MOF coating optimized the electrical field, inhibited the cracks, and reduced the Zn dendrite formation even at a high rate of 50 mAh/cm², due to the construction of electrolyte-philic and smooth surface. Consequently, the hygroscopic Zn/V-MOF symmetrical cells achieve exceptional performance over 1000 h under 50 mA/cm² (50 mAh/cm²) with 85.5% DOD. The Zn/V-MOF||V₂O₃/NC cell shows a capacity of 267 mAh/g at 0.5 A/g with excellent rate capability (100 mAh/g @20 A/g). In addition, it achieves an outstanding lifetime over 3300 cycles @ 5 A/g. The results at high rates with high DOD highlight the magnificent potential of hygroscopic V-MOF to achieve outstanding Zn anode and large-scale aqueous batteries.