The synthesis of a pentadentate ligand with strategically designed fluorinated arene groups in the second coordination sphere of a nonheme iron center is reported. The oxidatively resistant fluorine substituents allow for the trapping and characterization of an Fe-IV(O) complex at -20 degrees C. Upon warming of the Fe-IV(O) complex, an unprecedented arene C-F hydroxylation reaction occurs. Computational studies support the finding that substrate orientation is a critical factor in the observed reactivity. This work not only gives rare direct evidence for the participation of an Fe-IV(O) species in arene hydroxylation but also provides the first example of a high-valent iron-oxo complex that mediates aromatic C-F hydroxylation.