This article describes the systemic investigation of the interface chemical and electronic properties of ultrathin Fe/Al multilayer structure (MLS) as a function of annealing temperature. For this purpose electron beam evaporated [Fe/Al](x15) ML samples have been prepared under ultrahigh vacuum conditions. The chemical and electronic information of the interfaces at different depth has been obtained from XPS technique. The core level study show a gradual change in the nature of the electronic bonding at the interface as a result of annealing. In particular, the MLS annealed at 200 degrees C and 400 degrees C clearly show shifts in the binding energy position of Fe-2p(3/2) core line towards higher energy and Al-2p(3/2) core line towards lower energy side as compared to as-deposited sample, suggesting the formation of FeAl alloy phase at the interface. Another important finding with annealing is that the intensity of peak corresponding to pure Al-2p increases and that of Fe-2p decreases as compared to as-deposited case. The increase in intensity of Al-2p core line suggests the migration of Al atoms towards the surface owing to annealing induced inter-diffusion. The corresponding valence band spectra show appreciable changes in the Fe-3d as well as Al-3s density of states due to strong hybridization of sp-d states at the Fermi level as a result of charge transfer and also provide strong evidence for FeAl alloy formation. (C) 2009 Elsevier B. V. All rights reserved.