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A systematic study of the iron–silicon interfaces formed upon preparation of (Fe/Si) multilayers has been performed by combination of modern and powerful techniques. Samples were prepared by thermal evaporation under ultrahigh vacuum onto a Si(1 0 0) substrate. The morphology of these films and their interfaces was studied by a combination of scanning transmission electron microscopy, X-ray reflectivity, angle resolved X-ray photoelectron spectroscopy and hard X-ray photoelectron spectroscopy. The Si-on-Fe interface thickness and roughness were determined to be 1.4(1) nm and 0.6(1) nm, respectively. Moreover, determination of the stable phases formed at both Fe-on-Si and Si-on-Fe interfaces was performed using conversion electron Mössbauer spectroscopy on multilayers with well separated Si-on-Fe and Fe-on-Si interfaces. It is shown that while a fraction of Fe remains as α-Fe, the rest has reacted with Si, forming the paramagnetic c-Fe1−xSi phase and a ferromagnetic Fe rich silicide (DO3 type phase). We conclude that the paramagnetic c-Fe1−xSi silicide sublayer is identical in both Si-on-Fe and Fe-on-Si interfaces, whereas an asymmetry is revealed in the composition of the ferromagnetic silicide sublayer., The financial support of the Spanish MINECOMAT2011-23791, the President of Russia Grant (NSh-1044.2012.2), RFFI Grant 13-02-01265, the Ministry of Education and Science of Russian Federation (14.604.21.0002 and 02G25.31.0043), Aragonese DGA-IMANA E34 (cofunded by Fondo Social Europeo) and that received from the European Union FEDER funds is acknowledged. L.B.R. acknowledges the Spanish MINECO FPU 2010 grant.