Overall, it is clear that both hydrodefluorination and aminodefluorination are feasible for a range of substrates using only a simple, readily commercially available phosphine as the catalysts. The product yields and reaction times are amongst the best observed for main-group catalysts for highly electron-poor fluoroarenes. The performance of this system is often better than in related geometrically constrained P(III)/P(V) systems, although the silane/solvent used there is different, suggesting that geometric constraints are not required for usable reactivity. The key features of the catalytic system described here, however, are simplicity and cost. As all reagents are commercially available and simple to handle there is no barrier to entry to these catalytic reactions, broadening their potential applicability in a range of settings.