Rate coefficients as a function of temperature have been measured for the first time for the gas-phase reactions of chlorine atoms with methyl chlorodifluoracetate (k₁) and ethyl chlorodifluoroacetate (k₂) using the relative rate technique. The experiments were carried out in a 1080 L photoreactor over the temperature range 287–313 K at a total pressure of 1000 ± 10 mbar of synthetic air using in situ FTIR spectroscopy to monitor reactants and products. The following Arrhenius expressions were obtained: k_(MCDFA+Cl) = (9.6 ± 5.1) × 10⁻¹² exp[−(1363 ± 79)/T] and k_(ECDFA+Cl) = (64.4 ± 29.7) × 10⁻¹² exp[−(1110 ± 68)/T]. The kinetic results are compared with previous experimental and theoretical studies. In addition, a product study of the reactions of Cl with methyl chlorodifluoracetate and ethyl chlorodifluoroacetate is reported. The results indicate that in the absence of NO_x the main fate of the alkoxy radicals formed after H-atom abstraction by Cl from the –CH₃ group in methyl chlorodifluoroacetate is reaction of the radical with O₂ to form the mixed anhydride CF₂ClC(O)OC(O)H. In the case of ethyl chlorodifluoroacetate the main fate of the alkoxy formed via H-atom abstraction by Cl from the –CH₂– entity in the ethyl group is α-ester rearrangement to produce chlorodifluoroacetic acid and the corresponding radical. The yields of chlorofluoracetic acid (CF₂ClC(O)OH) obtained were as follows: (34 ± 5)% and (86 ± 8)% for the reactions of Cl with CF₂ClC(O)OCH₃ and CF₂ClC(O)OCH₂CH₃, respectively. The measured yields are rationalized in terms of mechanisms consisting of competitive reaction channels for the formed products in the oxidation, i.e. reaction with O₂, α-ester rearrangement and a decomposition pathway. Atmospheric implications are discussed according to the rate coefficients obtained as a function of temperature and altitude, and regarding the formation of chlorofluorocarboxylic acid.