Irradiation (λ > 320 nm) of ferrocene in chloroform causes decomposition of chloroform and the accumulation of HCl, CCl3OOH, and C2Cl6. This appears to occur initially through a cycle in which (a) ferrocene is oxidized to ferrocenium and tetrachloroferrate ions, (b) FeCl4 − undergoes photodissociation, and (c) ferrocenium reoxidizes the chloroferrate(II) species. On extended photolysis, the concentrations of CCl3OOH and FeCl4 − build up and a competing cycle in which FeCl4 − is restored through oxidation of the chloroferrate(II) species by CCl3OOH accelerates the decomposition rate.