Detailed investigations of the interaction of 1,2-diaminoethane with aluminium surfaces have been performed to understand the mechanisms of interphase formation in epoxy-amine/aluminium joints. In particular, it has been shown that both metal bond surface complexes (O-Al center dot center dot center dot N bonds) and hydrogen-bonded surface complexes (Al-OH center dot center dot center dot N and CxOyHz center dot center dot center dot N bonds) can be formed on aluminium surfaces covered with a partly contaminated (hydr) oxide film. However, surface dissolution can only be induced by mononuclear bidentate metal bond surface complexes (chelates), which result from a ligand exchange mechanism between specific hydroxyl sites (eta(1)- and mu(2)-OH) of the surface and the amino terminations of the molecule. The formation of these chelates weakens the trans Al-O bonds and detachment of the ligand-metal complexes can occur. This mechanism is enhanced by the presence of moisture. In practical epoxy-amine= aluminium joints, the interphase can, thus, be formed by migration of these complexes in the liquid polymeric phase before curing is achieved.