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 epitaxial growth of a Gd film is studied here by preparing trilayer systems of Fe/Cr/Gd on MgO(100) substrates by molecular-beam epitaxy (MBE). The thickness of the Cr interlayer was varied between 3-5 monolayers. The structural quality of the samples was confirmed by in-situ RHEED and ex-situ XRD measurements. Epitaxial Cr(001)/Fe(001) growth was observed, as expected. By use of 57 Fe-CEMS (Conversion Electron Mössbauer Spectroscopy) in combination with the 57 Fe 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(0001) Cr(001), with domains of the hexagonal Gd basal planes randomly oriented in the sample plane and not in registry with the underlying Cr(001) 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 is investigated by first principles theory.