Pulse radiolysis transient UV absorption spectroscopy was used to study the ultraviolet absorption spectra (230-330 nm) and kinetics of CF3C(O)OCH(.)CF, and CF3C(O)OCH(OO .)CF3 radicals at 296 K. At 280 nm sigma(CF3C(O)OCH(.)CF3) = (1.08 +/- 0.13) x 10(-18) cm(2) molecule(-1), at 240 nm sigma(CF3C(O)OCH(OO .)CF3) (2.06 +/- 0.24) x 10(-18) cm(2) molecule(-1). Rate constants for the reaction of F atoms with CF3C(O)OCH2CF3, the self-reactions of CF3C(O)OCH(.)CF3 and CF3C(O)OCH(OO)CF3 radicals, and the reactions of CF3C (O)OCH(OO)CF3 radicals with NO and NO2 were (1.8 +/- 0.2) x 10(-12), (1.5 +/- 0.2) x 10(-11), (7.6 +/- 0.9) x 10-12, (1.5 +/- 0.2) x 10(-11) and (8.5 +/- 0.9) x 10(-12) cm(3) molecule(-1) s(-1), respectively. The atmospheric fate of CF3C(O)OCH(O .)CF3 radicals was investigated in a FTIR smog chamber. Three loss processes for the CF3C(O)OCH(O .)CF3 radicals were identified at 296 K and 700 Torr total pressure, reaction with O-2 to form CF3C(O)OC(O)CF3, alpha-rearrangement to form CF3C(O). radicals and CSC(O)OH, and decomposition via a mechanism which is unclear. In 760 Torr of air at 296 K, 65% of the CF3C(O)OCH(O .)CF3 radicals react with oxygen, 18% undergo alpha-rearrangement, while the fate of the remaining 17% is unclear.