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The three-dimensional (3D) distribution of individual atoms on the surface of catalyst nanoparticles plays a vital role in their activity and stability. Optimising the performance of electrocatalysts requires atomic-scale information, but it is difficult to obtain. Here, we use atom probe tomography to elucidate the 3D structure of 10 nm sized Co₂FeO₄ and CoFe₂O₄ nanoparticles during oxygen evolution reaction (OER). We reveal nanoscale spinodal decomposition in pristine Co₂FeO₄. The interfaces of Co-rich and Fe-rich nanodomains of Co₂FeO₄ become trapping sites for hydroxyl groups, contributing to a higher OER activity compared to that of CoFe₂O₄. However, the activity of Co₂FeO₄ drops considerably due to concurrent irreversible transformation towards Co^IVO₂ and pronounced Fe dissolution. In contrast, there is negligible elemental redistribution for CoFe₂O₄ after OER, except for surface structural …