Nano-thermites， as one kind of energetic composites， have wide applications. A systematic study on the relationship between the interface structures and properties has great significance for the preparation of the new nano-thermites with excellent performance. The structures and energies of Fe₂O₃（104） and Fe₂O₃（110） surfaces and the structures， bonding properties， and adhesion work of Al（111）/Fe₂O₃（104） and Al（111）/Fe₂O₃（110） interfaces （AFS1， AFS2， AFS3， AFS4 and AFS5） were studied with the periodic density functional theory in this work. Results show that O-terminated Fe₂O₃（104） and Fe₂O₃（110） surfaces and the interfaces formed by these surfaces with Al（111） are more stable than those of the （104） and （110） surfaces of Fe₂O₃ respectively. Among 5 of the Al/Fe₂O₃ interfaces， the interfaces composed by the O-terminated Fe₂O₃（104） and Fe₂O₃（110） surfaces with Al（111）， i.e.， AFS1 and AFS5， have the maximum adhesion work （3.92 J·m^-2 and 3.02 J·m^-2， respectively）， and AFS1 is more stable than AFS5. In these two most stable interfaces， the Al atoms stack on the top position of the O atoms of the Fe₂O₃ surfaces and the binding of Al and Fe₂O₃ surfaces is mainly through the Al-O ionic bonds.