The Co(acac)2-catalyzed three-component difluoroalkylation-peroxidation of alkenes with difluorohaloactates and hydroperoxides has been developed. The protocol provides an efficient and selective access to various β-peroxyl difluoroalkyl derivatives, which can be transformed into α-amino acid and pyrimidine derivatives by the reactions with amines and amidines. The mild reaction conditions, broad substrate scopes, gram-scale synthesis, and synthetic applications exemplified the utility and practicability of this method. In addition, this methodology can be extended to other halide compounds to give the alkylation-peroxidation products.