<p>In this paper, a composite (NVO(210)-1.5Na) with three-phase composites of NaV₃O₈·xH₂O, NH₄V₄O₁₀, and V₅O₁₂·6H₂O has been successfully prepared by a one-step hydrothermal method induced by utilizing the inorganic salt Na₂HPO₄. NVO(210)-1.5Na combines the dual advantages of Na⁺ intercalation and heterostructure construction, showing superior electrochemical and kinetic properties. The layered structure provided by NH₄V₄O₁₀ and V₅O₁₂·6H₂O therein facilitates the structural stability of the material. NaV₃O₈·xH₂O possesses an open structure capable of accommodating the volumetric variations induced by Zn²⁺ deintercalation. Moreover, the first Na⁺ intercalation plays a crucial role in structural stabilization, thereby reducing the risk of framework collapse or mechanical degradation over repeated cycles. When used as cathode material for aqueous zinc ion batteries, NVO(210)-1.5Na provides a maximum discharge specific capacity of 346 mAh g⁻¹ at a current density of 0.3 A g⁻¹, and a stable capacity of 305 mAh g⁻¹ after 700 cycles, with a capacity retention rate as high as 88%. More surprisingly, NVO(210)-1.5Na still has a capacity retention rate of 67% after 5000 cycles at a current density of 1.0 A g⁻¹, and can be stably and efficiently cycled for more than 2000&#xa0;h, which confers the vanadium-based material with even better long-cycle stability at low current density.</p>