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Chemically sharp interface was obtained on single phase single oriented Fe3O4 (001) thin film (7 nm) grown on NiO (001) substrate using oxygen assisted molecular beam epitaxy. Refinement of the atomic structure, stoichiometry, and oxygen vacancies were determined by soft and hard x-ray photoelectron spectroscopy, low energy electron diffraction and synchrotron based X-ray reflectivity, and X-ray diffraction. Our results demonstrate an epitaxial growth of the magnetite layer, perfect iron stoichiometry, absence of oxygen vacancies, and the existence of an intermixing free interface. Consistent magnetic and electrical characterizations are also shown. The authors would like to acknowledge the ESRF and SpLine staff for their valuable help and financial support, also the Spanish MINECO and Consejo Superior de Investigaciones Científicas under Grant Nos. MAT2011-23785 and 20106OE013.