Abstract: A novel perfluoropolyether containing 0.1 to 10% by weight of halogen atoms as bonded in the molecule is obtained by reacting tetrafluoroethylene with oxygen in a fluorinated solvent or a chlorofluorinated solvent under ultraviolet irradiation in the presence of a halogenated hydrocarbon chain transfer agent having a chain transfer coefficient with respect to methyl methacrylate of at least 5.times.10.sup.-4.