Aqueous battery systems feature high safety, but they usually suffer from low voltage and low energy density, restricting their applications in large-scale storage. Here, we propose an electrolyte-decoupling strategy to maximize the full potential of Zn–MnO2 batteries by simultaneously enabling the optimal redox chemistry of both the Zn and MnO2 electrodes. The decoupled Zn–MnO2 battery exhibits an open-circuit voltage of 2.83 V (in contrast to the typical voltage of 1.5 V in conventional Zn–MnO2 batteries), as well as cyclability with only 2% capacity fading after deep cycling for 200 h. Benefiting from the full utilization of MnO2, the Zn–MnO2 battery is also able to maintain approximately 100% of its capacity at various discharge current densities. We also demonstrate the feasibility of integrating the Zn–MnO2 battery with a wind and photovoltaic hybrid power generating system. This electrolyte-decoupling strategy is shown to be applicable for other high-performance zinc-based aqueous batteries such as Zn–Cu and Zn–Ag batteries.