Complexes of chlorine atoms and carbon disulfide (CS2) were produced by pulse radiolysis of CS2 in halocarbons and photochemical reactions were studied by laser flash photolysis. Excitation of CS2/Cl complexes resulted in rapid and permanent photobleaching. The photobleaching of CS2/Cl complexes is due to intermolecular chlorine atom abstraction in CCl4 with a quantum yield of 0.04, while that ascribed to hydrogen atom abstraction in 1,2-dichloroethane has a quantum yield of 0.21. The effects of additives are discussed based on the bond dissociation energy