The interfacial structure and interactions of amine-cured epoxy resin (EP) / aluminium oxidie system were investigated in this presentation. The competitive chemisorption of uncured epoxy resin on Al2O3 particles were measured by FTIR and XPS. The interphase structure and the morphology at different depths of the broken-surface of the samples were characterized by XPS and SEM. The results showed that the nitrogenous molecules in the system formed the adsorbed monolayers on the interface based on the coupling interaction of the adsorption and cure. The composition, binding energy and chemical properties of the interphase deviated considerably from that of the bulk.