Synchrotron radiation soft x‐ray photoemission spectroscopy was used to investigate the native oxide ofn‐type single‐crystal CuInSe2. Photoemission measurements were acquired on the oxide surface before and after removal using sputter etching. Observed changes in the valence‐band electronic structure as well as changes in the In 4dand Se 3dcore lines were correlated with the interface chemistry at the oxide/CuInSe2interface. These results show the native oxide to be composed of an In2O3outer layer (no SeO2) with an additional Cu2Se interface layer.