The “as‐cast” microstructure of Fe–30Al–6Cr and Fe–30Al–10Ti high purity alloys was investigated using Electron Backscatter Diffraction. The first alloy is characterized by a highly textured columnar grain microstructure with large grains, while the second is characterized by an equiaxed grain microstructure with small grains and a random texture. These differences are discussed with regard to the higher reactivity of Ti compared with Cr, leading to nanometric nitride or oxide, which may act as sites for heterogeneous nucleation, and the ordered state of the BCC phase in equilibrium with the liquid during solidification and its effect upon dendrite growth kinetics. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)