A convenient and efficient copper-catalyzed three-component difluoromethylation-peroxidation of alkenes with commercially-available sodium difluoromethanesulfinate and tert-butyl hydroperoxide has been developed. This protocol enables the synthesis of a variety of β-difluoromethyl peroxides under mild conditions. Versatile synthetic transformations of the difluoromethyl peroxides have also been explored.