Epitaxial, coherent Mo/V multilayers were deposited by magnetron sputtering on (001) oriented MgO substrates at 873K (sample MoV-T), 923K (sample MoV-U) and 973K (sample MoV-V), respectively. In order to estimate the concentration profiles in our multilayers, a superlattice refinement modelling procedure has been used on high-angle XRD symmetric scans. The Mo/V interfaces were always sharper than V/Mo ones (in this notation the order of element reflects the sequence of deposition: e.g. the Mo/V interface was formed by the deposition of the V on the Mo surface). Furthermore the interface diffuseness was only slightly different at the lowest substrate temperature, but the difference increased with increasing temperature and an abrupt concentration jump could be observed at the Mo/V interface in the sample, sputtered at the 973 K. This indicates that during deposition the interfacial mixing by impact exchange events is important and thermally activated processes (surface diffusion and/or jumps driven by segregation) are less effective. With increasing substrate temperature the thickness of the V/Mo interfaces were unchanged while the Mo/V interface became shaper and sharper i.e. thermally activated jumps were more active during deposition of V atoms. Thus in forming Mo/V interfaces the segregation tendency of V to the Mo surface results in enhanced exchanges between V atoms (buried in the near surface layers of the Mo substrate) and surface Mo atoms, leading to more sharper interface with increasing temperature. On the other hand during the formation of the V/Mo interfaces the chemical thickness of the interface, provided again by impact exchanges, was practically unchanged.