In conclusion, we have developed a Ni-catalyzed exhaustive hydrodefluorination of perfluoroalkyl arenes using hydrosilanes as reductants. Mechanistic studies revealed that the reaction proceeds via benzylic hydrodefluorination, nickel-promoted elimination of HF, C(sp 2 )-F bond hydrodefluorination, hydrosilylation of the alkene, and protonation of the benzylsilane with trace amounts of water. The Ni(0)/ICy catalyst plays multiple roles in the reaction, enabling the unprecedented hydrodefluorination of non-benzylic C-F bonds mediated by a transition-metal complex.