The surface and near-surface chemical composition of electroceramic materials often shows significant deviations from that of the bulk. In particular, layered materials, such as cation-ordered LnBaCo₂O_5+δ perovskites (Ln = lanthanide), undergo surface and sub-surface restructuring due to the segregation of the divalent alkaline-earth cation. These processes can take place during synthesis and processing steps (e.g. deposition, sintering or annealing), as well as at temperatures relevant for the operation of these materials as air electrodes in solid oxide fuel cells and electrolysers. Furthermore, the surface segregation in these double perovskites shows fast kinetics, starting at temperatures as low as 400 °C over short periods of time and leading to a decrease in the transition metal surface coverage exposed to the gas phase. In this work, we use a combination of stable isotope tracer labeling and surface-sensitive ion beam techniques to study the oxygen transport properties and their relationship with the surface chemistry in ordered LnBaCo₂O_5+δ perovskites. Time-of-Flight Secondary-Ion Mass Spectrometry (ToF-SIMS) combined with ¹⁸O isotope exchange was used to determine the oxygen tracer diffusion (D*) and surface exchange (k*) coefficients. Furthermore, Low Energy Ion Scattering (LEIS) was used for the analysis of the surface and near surface chemistry as it provides information from the first mono-atomic layer of the materials. In this way, we could relate the compositional modifications (e.g. cation segregation) taking place at the electrochemically-active surface during the exchange at high temperatures and the oxygen transport properties in double perovskite electrode materials to further our understanding of the mechanism of the surface exchange process.