Thermoelectric half-Heusler compounds with the nominal composition (Ti0.33Zr0.33Hf0.33)NiSn were synthesized and exposed to operating conditions, i.e., elevated temperatures and oxidizing atmosphere. As-prepared samples were found to be a stable multiphase system consisting of Ti- and (Zr,Hf)-rich phases with half-Heusler structure. The influence of an oxidizing atmosphere at elevated temperatures on the sample was studied in- and ex situ by optical and electron microscopy and thermal analysis. Exposure to air resulted in surface oxidation starting at T = 545 K. During a defined heat treatment the Ti-rich phase decomposed while the (Zr,Hf)-rich phase was stable. In situ Atomic Force Microscopy and Scanning Kelvin Probe Force Microscopy experiments confirmed that interfaces, especially grain boundaries, are most prone to phase decomposition.