Perfluoroalkyl compounds that contain at least one CF3 or difluoromethylene group are recognized as persistent environmental pollutants. Many organofluorine compounds have been produced in the chemical industry, as their unique chemical, physical, and physiological properties have found various applications in pharmaceuticals, agrochemicals, surfactants, refrigerants, and polymers. One of the most remarkable properties of perfluoroalkyl substances is their chemical and thermal stability, which is derived from the strong C(sp )-F bonds. However, the inertness of these materials hampers their destruction. The continuous environmental release of perfluoroalkyl substances has resulted in their ubiquity as persistent pollutants in air, water, and soil. Some perfluoroalkyl gases show high global warming potentials, while others have been reported to accumulate in living organisms, including human beings. Therefore, the development of efficient decomposition methods is in urgent demand. The incineration of perfluoroalkyl substances requires very high temperatures and has the potential to produce volatile organofluorine waste. Other disposal methods are currently under intense investigation. For instance, recently, a mild homogeneous mineralization of Nickel-catalyzed exhaustive hydrodefluorination of perfluoroalkyl arenes 3 perfluoroalkanoic acids with sodium hydroxide in DMSO has been developed. Hydrodefluorination is a potential alternative disposal method for perfluoroalkyl compounds. The replacement of all the fluorine atoms of a perfluoroalkyl substance with hydrogen atoms produces a hydrocarbon, which can be disposed of using common methods such as burning or biodegradation. A large number of hydrodefluorination reactions have been developed following the seminal paper of Milstein using homogeneous catalysis. However, it should be noted here that most of the hydrodefluorination reactions reported to date involve the conversion of C(sp 2 )-F bonds, and that the C(sp 3 )-F bonds of perfluoroalkyl groups are more stable than those of monofluoroalkanes. The occurrence of dipolar resonance structures as well as steric shielding of carbon centers by fluorine atom(s) are obstacles to the ready transformation of C-F bonds in perfluoroalkyl groups. One example of such a hydrodefluorination of aliphatic C-F bonds is that reported by Jones using a stoichiometric amount of a Zr hydride complex, in which the reduction of CF3 was sluggish. Scheme 1. Hydrodefluorination reactions. A. Hydrodefluorination of CF3. B.