By magnetic coupling of Fe and Gd via Cr interlayers, the large local moment of Gd can be combined with the high Curie temperature of Fe. The textured growth of a Gd film is studied here by preparing trilayer systems of Fe/Cr/Gd on MgO(1 0 0) substrates by molecular-beam epitaxy (MBE). The thickness of the Cr interlayer was varied between 3 and 5 monolayers. The structural quality of the samples was confirmed by in situ RHEED and ex situ XRD measurements. Epitaxial Cr(0 0 1)/Fe(0 0 1) growth was observed, as expected. By use of 57Fe-CEMS (conversion electron Mössbauer spectroscopy) in combination with the 57Fe tracer layer method the Fe/Cr interface could be examined on an atomic scale and well separated Fe/Gd layers for all Cr thicknesses were confirmed. The unusual Gd/Cr crystallographic relationship of Gd(0 0 0 1)∥Cr(0 0 1), with domains of the hexagonal Gd basal planes randomly oriented in the sample plane and not in registry with the underlying Cr(0 0 1) lattice, was found from combined RHEED and x-ray measurements. Annealing of the samples resulted in a remarkable improvement of the crystalline structure of the Gd layers. On the other hand, the appearance of a single line in the CEM spectrum leads to the conclusion that during annealing a small amount of Fe diffuses into the Cr layer. The electronic structure and magnetism of this system are investigated by first-principles theory.