Perfluoroalkyl compounds are persistent environmental pollutants due to their strong C(sp3)-F bonds. Hydrodefluorination has emerged as a potential alternative disposal method for perfluoroalkyl compounds. Although the transformation of trifluoromethyl arenes into the corresponding methyl arenes has been studied by several research groups, hydrodefluorination reactions of longer perfluoroalkyl chains remain rare. Herein, we report exhaustive hydrodefluorination reactions of pentafluoroethyl arenes and longer-chain analogues using molecular nickel catalysis. Despite the cleavage of multiple C(sp3)-F bonds, the reaction already proceeds upon gentle heating (60 °C). A mechanistic investigation indicated that the reaction proceeds via benzylic hydrodefluorination reactions followed by homobenzylic ones. We reveal the multiple roles of the Ni catalyst, which include C-F bond cleavage, promotion of HF elimination, and hydrosilylation.