This work is part of an ongoing European funded project, SMILER, with the aim of improving the performance of alumina forming Fe-20Cr-5Al-Y alloys for high temperature industrial applications. One aspect of the project is to investigate the influence of additives on the oxidation behaviour of these alloys. During this study a LEO 1550 FESEM (field emission scanning electron microscope), equipped with INCA X-ray microanalysis facilities was used. Ultra-high-purity model alloys, where the levels of additives (Hf, Zr, Ti, Si, La and Y) were carefully controlled, and two commercial Aluchrom YHfAl and Kanthal AMPT alloys were oxidised at 1200°C for up to 3100h (100h/cycle). The YHfAl, (Y+Ti+Zr)- and (Y+Zr+Hf)-containing alloys showed the highest oxidation rates when oxidised, whereas the La-containing alloy showed the lowest oxidation rate. However, the La-containing alloy spalled the most, while the (Y+Zr+Hf)-containing and YHfAl alloys showed little spallation, and the additives appeared to have a major influence on the spallation of the α-alumina scale formed. On the alloys with La and Si respectively, the scale spalled at the scale/metal interface (adhesively), whereas on alloys containing (Y+Hf+Ti) and (Y+Hf+Zr) and the YHfAl alloy, the scale spalled mainly in a cohesive manner (within the scale). Also, the added elements affected the scale topography. In general the scale had a columnar structure at the scale/metal interface, whereas the grains were equiaxed at the scale/gas interface. However, in the case of YHfAl and (Y+Zr+Hf)-containing alloys, a sunflower type structure was observed in both fractured samples, in the regions where the scale spalled cohesively. Preliminary EDX analyses revealed that, in the case of YHfAl, for example, the center of the sunflower structure was rich in Mg. This suggests that there may be inhomogeneities in the metal substrate, prior to oxidation, where high concentrations of Mg increase the local oxide growth rate.