Synchrotron radiation photoemission spectroscopy was used to study the formation process of Er2O3/Si(001) interface and film during epitaxial growth on Si. A shift in the O core-level binding energy was found accompanied by a shift in the Er2O3 valence band maxi-mum. This shift depended on the oxide layer thickness and interfacial structure. An interfacial layer was observed at the initial growth of Er2O3 film on Si, which was supposed to be attributed to the effect of Er atom catalytic oxidation effect.