A smog chamber/FTIR technique was used to study the Cl atom initiated oxidation of CF3OCH3 in 700 Torr of N-2/O-2 at 296 K. Using relative rate techniques it was determined that k(Cl + CF3OCH3) = (1.4 +/- 0.2) x 10(-13) and k(Cl + CF3OC(O)H) = (9.8 +/- 1.2) x 10(-15) cm(3) molecule(-1) s(-1). At 700 Torr of N-2/O-2 diluent at 296 K reaction with O-2 is the only loss mechanism of the CF3OCH2O. radical. The infrared spectra of the peroxy nitrates CF3OCH2O2NO2 and CF3OC(O)O2NO2 were recorded and compared to the nonfluorinated analogues CH3OCH2O2NO2 and CH3OC(O)O2NO2. The thermal decomposition rate of CF3OC(O)O2NO2 is (2.3 +/- 0.1) x 10(-4) s(-1) in 700 Torr of N-2 at 295.8 K. The reaction of CF3OC(O)O-2 radicals with HO2 radicals gives CF3OC(O)H in a yield of (80 +/- 11)%. The results are discussed with respect to the atmospheric degradation mechanism of CF3OCH3 and other ethers.