Two‐step growth of an AlInSb film mediated by an InSb bi‐layer on a Si(111) substrate was performed in a molecular beam epitaxy (MBE) chamber. The growth was observed by in situ reflection high energy electron diffraction. After the deposition, the samples were characterized by X‐ray diffraction (XRD). It is confirmed that the grown AlInSb films were rotated by 30° with respect to the Si substrates. The lattice mismatch between the AlInSb and the Si substrate was reduced by the rotation. Using this method, epitaxial AlyIn(1‐y)Sb layers which have the composition ratio y of 0.22‐0.65 can be achieved without thick buffer layers. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)