The aqueous multivalent metal-ion (Mⁿ⁺ (n denotes the valence/charge number of metal (M) ion, n ≥ 2)) battery is a promising new generation of electrochemical energy storage systems. This battery has several advantages, such as low cost, high safety, and high capacity. However, the acidic aqueous electrolyte environment and the large ionic radius of multivalent metal ions tend to cause failure of the positive electrode structure during cycling. This failure results in a long-term shortage of electrode materials suitable for the reversible storage of multivalent metal ions, severely restricting the development of this system. To address this key bottleneck, this study systematically examines two representative studies conducted by our research group on vanadium-based electrode materials and successfully verifies them in different battery systems. (1) The core achievement is the “Zn²⁺-mediated water dissociation interfacial catalytic storage model”. In aqueous zinc-ion batteries using VN@rGO (three-dimensional porous reduced graphene oxide (rGO) aerogel confined vanadium nitride (VN) nanocrystals) cathodes, Zn²⁺ can polarize interfacial H₂O molecules and induce water dissociation. This enables the generated *OH (where * denotes adsorption sites on the cathode surface) intermediates to undergo reversible adsorption/desorption on vanadium-based interfaces and participate in fast charge storage. This model transforms H₂O in aqueous batteries from a potential source of parasitic reactions into a tunable participant in energy-storage reactions, thereby providing a new perspective on their fast-charging behavior that differs from the conventional ion intercalation/deintercalation and pseudocapacitive mechanisms. Experimental results demonstrate that the Zn²⁺-VN coordination system achieves the theoretically predicted optimal balance between *OH adsorption and desorption. (2) As an extension of this interfacial water/proton chemistry, monoclinic VO₂ nanorod electrodes with tunnel structures are further applied in aqueous manganese-ion batteries to realize efficient Mn²⁺ storage. This storage efficiency is achieved via a reversible ion intercalation/deintercalation mechanism. Thus, this study reveals the Mn²⁺/H⁺ cointercalation behavior and clarifies the intrinsic mechanism of irreversible vanadium dissolution induced by high proton activity. Based on these results, a hydrogen-bond reconfiguration-driven proton-transfer regulation strategy is proposed to optimize the electric double-layer structure at the electrode/electrolyte interface, effectively suppress excessive interfacial proton activity and side reactions, and enable the VO₂ electrodes to achieve excellent rate performance and cycling stability. This work indicates that the development of aqueous multivalent metal-ion batteries requires high-capacity electrode materials and coordinated storage chemistry system involving metal ions, H₂O molecules, and electrode interfaces.