The complex Cp*Rh(PMe3)H-2 (Cp* = C5Me5) reacts with C6F6, C6F5H, C12F10 or C10F8 in pyridine or 1:1 pyridine/benzene to give the C-F cleavage products Cp*Rh(PMe3)(aryl(F))H in high yield. Kinetic studies reveal that the reaction has autocatalytic character, and fluoride ion is shown to be responsible for the catalysis. The anion [Cp*Rh(PMe3)H](-) reacts rapidly with C12F10 or C10F8 to give the same C-F cleavage products as Cp*Rh(PMe3)H-2. A mechanism initiated by deprotonation of Cp*Rh(PMe3)H-2 followed by nucleophilic attack of the resulting anion on the polyfluoroaromatic with subsequent loss of fluoride is proposed. The fluoride ion continues the cycle by deprotonating Cp*Rh(PMe3)H-2.