Transition metal fluoride complexes are of interest because they are potentially useful in a multitude of catalytic applications, including C-F bond activation and fluorocarbon functionalization. We report the first crystallographically characterized examples of molecular iron(II) fluorides: [(LFe)-Fe-Me(mu-F)](2) (1(2)) and (LFeF)-Fe-tBu (2) (L = bulky beta-diketiminate). These complexes react with donor molecules (L'), yielding trigonal-pyramidal complexes (LFeF)-Fe-R(L'). The fluoride ligand is activated by the Lewis acid Et2O center dot BF3, forming (LFe)-Fe-tBu(OEt2)(eta(1)-BF4) (3), and is also silaphilic, reacting with silyl compounds such as Me3SiSSiMe3, Me3SiCCSiMe3, and Et3SiH to give new thiolate (LFeSSiMe3)-Fe-tBu (4), acetylide (LFeCCSiMe3)-Fe-tBu (5), and hydride [(LFe)-Fe-Me(mu-H)](2) (6(2)) complexes. The hydrodefluorination (HDF) of perfluorinated aromatic compounds (hexafluorobenzene, pentafluoropyridine, and octafluorotoluene) with a silane R3SiH (R-3 = (EtO)(3), Et-3, Ph-3, (3,5-(CF3)(2)C6H3)Me-2) is catalyzed by addition of an iron(II) fluoride complex, giving mainly the singly hydrodefluorinated products (pentafluorobenzene, 2,3,5,6-tetrafluoropyridine, and alpha,alpha,alpha,2,3,5,6-heptafluorotoluene, respectively) in up to five turnovers. These catalytic perfluoroarene HDF reactions proceed with activation of the C-F bond para to the most electron-withdrawing group and are dependent on the degree of fluorination and solvent polarity. Kinetic studies suggest that hydride generation is the rate-limiting step in the HDF of octafluorotoluene, but the active intermediate is unknown. Mechanistic considerations argue against oxidative addition and outer-sphere electron transfer pathways for perfluoroarene HDF. Fluorinated olefins are also hydrodefluorinated (up to 10 turnovers for hexafluoropropene), most likely through a hydride insertion/beta-fluoride elimination mechanism. Complexes 12 and 2 thus provide a rare example of a homogeneous system that activates C-F bonds without competitive C-H activation and use an inexpensive 3d transition metal.