We report on a structural study of Si/Ge multilayers grown by molecular‐beam epitaxy on (100)‐Si substrates. The analyses have been performed by using transmission electron microscopy, high‐resolution x‐ray diffraction, and secondary‐ion‐mass spectrometry. The investigated specimens differ in number of periods, period thickness, and in the Si/Ge periods thickness ratio. In particular, we investigate the interdiffusion of the Ge atoms in each superlattice period of the epilayer and in the epilayer as whole. The interdiffusion causes a broadening of the nominal thickness of the Ge layer producing a SixGe1−xalloy. Furthermore, the Ge content in the multilayer periods increases as a function of the growth time, i.e., the superlattice periods close to the sample surface contain more Ge atoms if compared to the periods close to the substrate/superlattice interface. We find two steps in the strain relaxation: (i) In each period the strain energy density is partially reduced by the formation of coherent islands; (ii) at a certain value of the strain energy density the shape of the islands changes and the structures relax partially or completely the accumulated strain energy by nucleation of extended defects. ©1996 American Institute of Physics.