This work provides a summary of progress in emerging areas of the science of materials interfaces and interface engineering of energy materials. The progress, which is focused on gas-solid reactivity of oxide materials, indicates that the high-temperature electron probe (HTEP) offers new insight into the local defect-related properties of the surface layer that are critical for understanding the reactivity of solids and the related charge transfer. The probe enables unequivocal surface characterization of energy materials in gas–solid equilibrium and in-situ surface monitoring during processing and performance at elevated temperatures. Specific progress has been achieved in understanding the impact of both chemisorption and surface segrega...