AbstractEpitaxial strain has been shown to produce dramatic changes to the orbital structure in transition metal perovskite oxides and, in turn, the rate of oxygen electrocatalysis therein. Here, epitaxial strain is used to investigate the relationship between surface electronic structure and oxygen electrocatalysis in prototypical fuel cell cathode systems. Combining high‐temperature electrical‐conductivity‐relaxation studies and synchrotron‐based X‐ray absorption spectroscopy studies of La_0.5Sr_0.5CoO₃ and La_0.8Sr_0.2Co_0.2Fe_0.8O₃ thin films under varying degrees of epitaxial strain reveals a strong correlation between orbital structure and catalysis rates. In both systems, films under biaxial tensile strain simultaneously exhibit the fastest reaction kinetics and lowest electron occupation in the d_z² orbitals. These results are discussed in the context of broader chemical trends and electronic descriptors are proposed for oxygen electrocatalysis in transition metal perovskite oxides.