Selecting the right cathode material is a key component to achieving high‐energy and long‐lifespan aqueous zinc‐ion batteries (AZIBs); however, the development of cathode materials still faces serious challenges due to the high polarization of Zn2+. In this work, MnV12O31·10H2O (MnVO) synthesized via a one‐step hydrothermal method is proposed as a promising cathode material for AZIBs. Because the stable layered structure and hieratical morphology of MnVO provide a large layer space for rapid ion transports, this material exhibits high specific capacity (433 mAh g−1 at 0.1 A g−1), an outstanding long‐term cyclability (5000 cycles at a current density of 3 A g−1), and an excellent energy density (454.65 Wh kg−1). To illustrate the intercalation mechanism, ex situ X‐Ray diffraction, Fourier transform infrared spectroscopy, and X‐ray photoelectron spectroscopy are adopted, uncovering an H+/Zn2+ dual‐cation co‐intercalation processes. In addition, density‐functional theory calculation analysis shows that MnVO has a delocalized electron cloud and the diffusion energy barrier of Zn2+ in MnVO is low, which promotes the Zn2+ transport and consequently improves the reversibility of the battery upon deep cycling. The key and enlightening insights are provided in the results for designing high‐performance vanadium‐oxide‐based cathode materials for AZIBs.