Among the perovskites used to catalyze the oxygen evolution reaction (OER), Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCF) exhibits excellent activity which is thought to be related to dynamic reconstruction at the flexible perovskite surface due to accommodation of large amount of oxygen vacancies. By studying the local structure and chemistry of BSCF surfaces, in detail, via a range of transmission electron microscopy (TEM) methods, we show that the surfaces of the as-synthesized BSCF particles are Co/Fe rich, and remarkably, adopt a spinel-like structure with a reduced valence of Co ions. Post-mortem and identical location TEM analyses reveal that the Co/Fe spinel-like surface retains a stable chemical environment of the Co/Fe ions, although its structure weakens after electrochemical processing. Further, it is verified that prior to the onset of OER, the Co/Fe spinel-like surface promotes the formation of the highly active Co(Fe)OOH phase, which enhances the OER electrocatalytic properties of the underlying conductive BSCF perovskite. This study provides a detailed understanding of the fundamental transformations that oxide catalysts undergo during electrochemical processes and can aid in the development of novel oxide catalysts with enhanced activity.