Bis(trifluoromethy1) peroxide is readily dissociated by multiple infrared photon excitation at COz laser wavelengths. The primary dissociation product is CF30; approximately 85% of the nascent radicals are further dissociated in the laser field to form CFzO and F. The F atoms then react with the remaining CF30 to produce CF30F. The formation of CF3OF is strongly inhibited by addition of HI, which reacts preferentially with the F atoms.