The oxygen evolution reaction (OER) is of prime importance in multiple energy storage devices; however, deeper mechanistic understanding is required to design enhanced electrocatalysts for the reaction. Current understanding of the OER mechanism based on oxygen adsorption on a metallic surface site fails to fully explain the activity of iridium and ruthenium oxide surfaces, and the drastic surface reconstruction observed for the most active OER catalysts. Here we demonstrate, using La2LiIrO6 as a model catalyst, that the exceptionally high activity found for Ir-based catalysts arises from the formation of active surface oxygen atoms that act as electrophilic centres for water to react. Moreover, with the help of transmission electron microscopy, we observe drastic surface reconstruction and iridium migration from the bulk to the surface. Therefore, we establish a correlation between surface activity and surface stability for OER catalysts that is rooted in the formation of surface reactive oxygen.