Sputter deposited symmetric multilayers of (n Fe)/(n Ni), with individual thicknesses from n = 4 to n = 48 monolayers (ML), were deposited on epitaxial Cu/Si(001), and their microstructural evolution and magnetic properties versus n have been studied. Elemental layering can be seen with transmission electron microscopy down to n = 4 ML layer thickness, although an intermixed region characterized by a finite interface width is found to be present. This width is composed of the interface roughness as well as the interdiffusion between layers, but the relative contributions from these two sources could not be concluded by the techniques used. The measured elemental layering and X-ray reflectivity (XRR) give an upper limit to the interface width which must be smaller than the thinnest layers, 4 ML. Electron energy loss spectroscopy (EELS), depth profiling X-ray photoelectron spectroscopy (XPS) and also XRR reveal that Fe has a higher tendency to mix with Ni than vice versa. XPS does not have the resolution to measure this thin elemental layering: composition variations for n = 8 ML which are clearly seen by EELS are barely resolved by XPS. The structure was determined by X-ray diffraction, and an epitaxial fcc (001) structure is found to be maintained throughout the multilayers up to n less than or similar to 8 ML. For larger n values, relaxation starts by Fe-fcc(001) layers changing into Fe-bcc(110), which is then followed by Ni-fcc(001) changing from (001) to (111) orientation along the growth direction. A decreased total measured magnetic moment for the fully epitaxial multilayers can be explained by the fcc Fe layers being partly anti-ferromagnetic, whereas the relaxed multilayers exhibit the expected magnetic properties of (bcc Fe) +(fcc Ni).