Homogeneous catalytic hydrodefluorination (HDF) of fluoroaromatics under thermal conditions was achieved using nickel(0) compounds of the type [(dippe)Ni-(eta(2)-C6F6-nHn)] where n = 0-2, as the catalytic precursors. These complexes were prepared in situ by reacting the compound [(dippe)Ni(mu-H)](2) with the respective fluoroaromatic substrate. HDF seems to occur homogeneously, as tested by mercury drop experiments, producing the hydrodefluorinated products. However, despite previous findings by other groups, we found that these HDF reactions were actually the result of direct reaction of the alkylphosphine with the fluoroaromatic substrate. This metal- and silane-free system is the first reported example of a phosphine being able to hydrodefluorinate on its own.