Controlling the structure of catalysts at the atomic level provides an opportunity to establish detailed understanding of the catalytic form-to-function and realize new, non-equilibrium catalytic structures. Here, advanced thin-film deposition is used to control the atomic structure of La_2/3Sr_1/3MnO₃, a well-known catalyst for the oxygen reduction reaction. The surface and sub-surface is customized, whereas the overall composition and d-electron configuration of the oxide is kept constant. Although the addition of SrMnO₃ benefits the oxygen reduction reaction via electronic structure and conductivity improvements, SrMnO₃ can react with ambient air to reduce the surface site availability. Placing SrMnO₃ in the sub-surface underneath a LaMnO₃ overlayer allows the catalyst to maintain the surface site availability while benefiting from improved electronic effects. The results show the promise of advanced thin-film deposition for realizing atomically precise catalysts, in which the surface and sub-surface structure and stoichiometry are tailored for functionality, over controlling only bulk compositions.