Compared to exhaustive hydrodefluorination reactions of trifluoromethyl groups, those of longer perfluoroalkyl chains are scarce. Ozerov has disclosed that a hydrodefluorination reaction of 1,1,1,2,2,3,3,4,4-nonafluorohexane with trihexylsilane proceeds under mild conditions (50 °C) using Ph3C[HCB11H5Cl6] as a catalyst. The carborane counter cation is essential to achieve the high turnover number (TON) through stabilization of the active cationic silyl species. The substrate scope for the perfluoroalkyl group, which was limited to this single example, prompted us to investigate the possibility of using a nickel catalyst for the hydrodefluorination of longer perfluoroalkyl chains.