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To examine the influence of the barrier quality in fully epitaxial Fe/MgO/Fe(001) magnetic tunnel junctions (MTJs), we propose to use Fe-V alloys as magnetic electrodes. This leads to a reduced misfit with MgO. We actually observe, by high-resolution electron microscopy (HREM) and local strain measurements, that the misfit dislocations density in the MgO barrier is lower when it is grown on Fe-V(001). This improvement of the crystalline quality of the MgO barrier actually leads to a significant increase of the tunnel magneto-resistance (TMR), despite the loss of spin polarization (SP) in these alloys, which was measured by spin-polarized X-ray photoelectron spectroscopy (SR-XPS).