Pulse radiolysis transient UV absorption spectroscopy was used to study the ultraviolet absorption spectra (220-320 nm) and kinetics of CF₃CH(·)OCH₂CF₃ and CF₃CH(OO·)OCH₂CF₃ radicals at 296 K. At 230 nm σ(CF₃CH(·)OCH₂CF3) = (1.95 ± 0.24) × 10^-18 and σ(CF₃CH(OO·)OCH₂CF₃) = (4.40 ± 0.51) × 10^-18 cm² molecule^-1. Rate constants for the reaction of F atoms with CF₃CH₂OCH₂CF₃, the self-reactions of CF₃CH(·)OCH₂CF₃ and CF₃CH(OO·)OCH₂CF₃ radicals, the association reaction of CF₃CH(·)OCH₂CF₃ radicals with O₂, and the reactions of CF₃CH(OO·)OCH₂CF₃ radicals with NO and NO₂ were (1.5 ± 0.7) × 10^-11, (2.6 ± 0.4) × 10^-11, (5.4 ± 0.7) × 10^-12 (uncorrected for possible secondary chemistry), (2.3 ± 0.3) × 10^-12, (1.45 ± 0.4) × 10^-11, and (8.4 ± 0.8) × 10^-12 cm³ molecule^-1 s^-1, respectively. Using an FTIR technique, rate constants for the reaction of Cl atoms with CF₃CH₂OCH₂CF₃ and CF₃C(O)OCH₂CF₃ were determined to be (7.1 ± 0.9) × 10^-13 and (9.4 ± 1.3) × 10^-16 cm³ molecule^-1 s^-1. Finally, it was determined that the atmospheric fate of CF₃CH(O·)OCH₂CF₃ radicals is decomposition via C-C bond scission to give CF₃ radicals and 2,2,2-trifluoroethyl formate (CF₃CH₂OCHO) which occurs at a rate of approximately 7 × 10⁵ s^-1. The results are discussed with respect to the atmospheric chemistry of CF₃CH₂OCH₂CF₃ and analogous compounds.