A target of Fe-40 at.-%Al intermetallic alloy with ordered B2 structure was subjected to laser melting processing by a high energy XeCI excimer pulse (wavelength 308 nm, pulse length 120 ns) in low pressure air. The total thickness of the laser affected zone (LAZ) was ∼ 150 nm. The modified surface showed an increased roughness and the presence of cracking. The X-ray photoelectron spectroscopy (XPS) measurements revealed a strong enrichment in the aluminium concentration within the LAZ, as well as relatively high contents of oxygen and nitrogen incorporated in the near surface region. Both angle resolved and depth profile XPS analyses suggested that oxides, nitrides, and oxynitrides were mainly present within the LAZ as discrete particles in the metallic matrix rather than as surface layers. Significant surface hardness reduction was observed after laser treatment, which has been interpreted to be due to partial suppression of B2 lattice ordering. Electrochemical measurements in borate buffer solution showed a reduced anodic activity of the laser processed aluminide in the potential range between the open circuit potential and 0.1 V saturated calomel electrode, whereas at higher anodic overpotentials no substantial differences in behaviourwere observed with respect to the untreated Fe–40Al surfaces. Such consequences of the excimer laser treatment may be explained by mechanisms involving aluminium enrichment and nitride formation processes inside the LAZ.