A pulse radiolysis technique has been used to measure a rate constant of (6.6±1.3) x 10^-12 cm³ molecule^-1 s^-1 for the association reaction between CF₃C(O)O₂ radicals and NO₂ at 295 K and one atmosphere total pressure of SF₆ diluent. A FTIR/smog chamber system was used to study the thermal decomposition CF₃C(O)O₂NO₂. The rate of decomposition of CF₃C(O)O₂NO₂ was independent of the total pressure of N₂ diluent over the range 100-700 Torr and was fit by the expression k_-1=(1.9_-1.5 ^+7.6)x10¹⁶ exp[(-14000±480)/T] s^-1. Implications for the atmospheric chemistry of CFC replacements are discussed.