Abstract We report the first example of gold catalyzing C [BOND] F bond activation for perfluoroarenes in the presence of silanes. Tricoordinated gold (I) complexes supported by Xantphos-type ligands, such as Xantphos and t BuXantphos ligands, exhibit efficacy in the hydrodefluorination (HDF) of various types of perfluoroarenes. For [t BuXantphosAu (AuCl 2)], the highest turnover number is up to 1000 in the HDF of pentafluoronitrobenzene with ...