Flash photolysis combined with time-resolved UV spectroscopy and transient infrared absorption is used to investigate the reactions of CF3C(O)O-2 with itself, CF3O2, and nitric oxide. The UV spectrum of CF3C(O)O-2 exhibits two bands, the stronger short wavelength component of which has a maximum cross section of 7.1 x 10(-18) cm(2) at 207 nm. These bands are used to monitor the disappearance of CF3C(O)O-2 and the secondary formation of CF3O2, yielding a self-reaction rate constant of (3.7(-2)(+5)) x 10(-12) e((270+/-200)/T) cm(3) s(-1). The cross reaction between CF3C(O)O-2 and CF3O2 is found to be slow, having a rate constant of less than or equal to 2 x 10(-12) cm(3) s(-1). Transient IR monitoring of the loss of NO and concomitant formation of NO2 leads to a rate constant of (4.0(-1.4)(+2.2)) x 10(-12) e((563+/-115)/T) cm(3) s(-1) for the reaction between CF3C(O)O-2 and NO. This result implies that CF3C(O)O-2 radicals formed as intermediates in the atmospheric degradation of hydrofluorocarbons (HFCs) are rapidly converted into CF3O2 radicals, which are in turn converted into carbonyl fluoride and FNO.