The invention is directed to a process for separating a mixture comprising hafnium and zirconium. The process of the present invention comprises a step in which a molten metal phase comprising zirconium and hafnium dissolved in a first metal M1 and a second metal M2 is contacted with a molten salt phase comprising at least one metal halide M3Z, wherein M3 is a metal that is less electropositive than zirconium and hafnium, and at least one salt of one or more metals M4, wherein M4 is a metal from Group 1 or Group 2 of the Periodic Table, whereby at least part of said hafnium is transported from said molten metal phase to said molten salt phase.