It has been possible to demonstrate that complex molecular architectures are not required to allow P(III) systems to act as catalysts for the HDF or aminodefluorination of highly fluorinated arenes and heterocycles. In fact, simple trialkylphosphines were found to be fast and effective catalysts for these reactions for a range of substrates, but especially those that are highly electron poor. This is an important observation as some trialkylphosphines, especially the P n Bu3 used here, are cheap, readily available from commercial suppliers and simple to handle. This eliminates the barrier to entry that exists for some main-group catalyst systems and so these reactions can be widely applied in a range of academic and industrial settings.