In acetonitrile and tetrahydrofuran solutions, irradiation of [ReBr6]2− leads to the replacement of a bromide by a solvent molecule, followed at a much slower rate by the photosolvation of a second bromide. The quantum yield for the primary photosolvation is 0.013 in CH3CN. As an alternative to photolysis occurring through a doublet d–d excited state, it is suggested that excitation of the charge transfer bands may cause photodissociation, followed by coordination of a solvent molecule and reoxidation to the final product.