Resonant anomalous X-ray reflectivity (RAXR) is a powerful technique for measuring element-specific distribution profiles across surfaces and buried interfaces. Here, the RAXR technique is applied to characterize a complex oxide heterostructure, La_0.6Sr_0.4Co_0.2Fe_0.8O_3−δ, on NdGaO₃, and the effects of data sampling and model-dependent fitting procedures on the extracted elemental distribution profile are evaluated. The strontium profile through a 3.5 nm-thick film at 973 K and at an oxygen partial pressure of 150 Torr (1 Torr = 133.32 Pa) was determined from the measured RAXR spectra. The results demonstrate thatin situRAXR measurements can provide key insights into temperature- and environment-dependent elemental segregation processes, relevant, for example, in assessing the cathode performance of solid oxide fuel cells.