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The oxygen electrode plays a vital role in the successful commercialization of renewable energy technologies, such as fuel cells and water electrolyzers. In this study, the Prussian blue analogue-derived nitrogen-doped nanocarbon (NC) layer-trapped, cobalt-rich, core-shell nanostructured electrocatalysts (core-shell Co@NC) are reported. The electrode exhibits an improved oxygen evolution activity and stability compared to that of the commercial noble electrodes. The core-shell Co@NC-loaded nickel foam exhibits a lower overpotential of 330 mV than that of IrO2 on nickel foam at 10 mA cm-2 and has a durability of over 400 h. The commercial Pt/C cathode-assisted, core-shell Co@NC-anode water electrolyzer delivers 10 mA cm-2 at a cell voltage of 1.59 V, which is 70 mV lower than that of the IrO2-anode water electrolyzer. Over the long-term chronopotentiometry durability testing, the IrO2-anode water electrolyzer shows a cell voltage loss of 230 mV (14%) at 95 h, but the loss of the core-shell Co@NC-anode electrolyzer is only 60 mV (4%) even after 350 h cell-operation. The findings indicate that the Prussian blue analogue is a class of inorganic nanoporous materials that can be used to derive metal-rich, core-shell electrocatalysts with enriched active centers. [ABSTRACT FROM AUTHOR]