Aqueous zinc-ion batteries (ZIBs) promise a few advantages: natural abundance and massive production; non‐toxic, easy and mature processing, high volumetric energy density (5851 mA h mL^-1), high stability and compatibility in aqueous electrolytes, and the two-electron-redox properties offer a high theoretical anode capacity (820 mA h g^-1). In spite of great progress made in recent years, some critical challenges remain to be addressed, such as dissolution of cathodes, formation of basic zinc salts, co-intercalation of protons, and large voltage gap of redox pairs. In this presentation, I will take vanadium pentoxide and hydrate vanadium pentoxide as model systems to demonstrate that the introduction of oxygen vacancies and pre-insertion of cations and organic complex can effectively reduce the charge-discharge polarization, resulting in much enhanced storage capacity, and high energy conversion efficiency with excellent cycling stability. Various possible mechanisms for the enhanced electrochemical properties and battery performance are discussed.