The ultraviolet absorption spectrum of the CF₃CFO₂CF₃ radical, the kinetics of its self-reaction and reactions. with NO and NO₂ have been studied in the gas phase at 296K using a pulse radiolysis technique. A long-path-length Fourier transform infrared technique was used to study the fate of the CF₃CFO'CF₃ radical. Absorption cross sections for the CF₃CFO₂'CF₃ radical were quantified over the wavelength range 220-270 nm. At 230 nm, a(CF₃CFO₂'CF₃) = (351 ±73) × 10^-20 cm² molecule^-1. The observed rate constant for the CF₃CFO₂'CF₃ self-reaction was (1.8 ±0.4) × 10^-12 cm³ molecule^-1 s^-1. The rate constants for the reaction of CF₃CFO₂'CF₃ radicals with NO and NO₂ were k₃ = (2.1 ±0.9) × 10^-11 and fc, = (4.8 ±1.4) × 10^-12 cm³ molecule^-1 s^-1. The atmospheric fate of CF₃CFO'CF₃ radicals is decomposition via C-C bond scission to give CF₃ radicals and CF₃C(O)F. In 1000 mbar of SF6 at 296 K decomposition of CF₃CFO'CF₃ radicals proceeds at a rate greater than 1 × 105 s^-1. As part of this work relative rate techniques were used to measure k(C1+CF₃CFHCF₃) = (4.5 ±1.2) × 10^-17 and k(F+CF₃CFHCF₃) = (1.5 ±0.5) × 10^-13 cm³ molecule^-1 s^-1. This compares well with the value of k(F+CF₃CFHCF₃) = (1.9 ±0.4) × 10^-13 cm³ molecule^-1 s^-1 obtained by pulse radiolysis. The results are discussed in the context of the atmospheric chemistry of HFC-227ea.