We report on the temperature dependence of optical response of pure bcc iron and CrNiAl steel. Ellipsometric spectra, covering the 1.4‐3.0 eV spectral range, have been obtained during temperature cycles reaching 650 °C in UHV chamber. Since the penetration depth of light is rather small and the data are sensitive to the quality of sample surfaces, we have examined polished, etched and annealed samples. We identify characteristic features of the temperature dependence, consisting in spectral shifts of interband transitions and a redistribution of spectral weight. We have also detected reproducible irreversible changes in the initial stages of annealing cycles when the samples are heated to at least 300 °C. With increasing temperature, we observe a pronounced reduction of the minority‐spin interband contribution. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)