The atmospheric fate of CF₃CO radicals has been studied using a pulse radiolysis technique to provide kinetic data and FTIR-smog chamber system to provide product data. In 1 atm of SF₆ at 296 ± 2 K, CF₃CO radicals decompose to give CF₃ radicals and CO with a rate of (1.2 ± 0.8) × 10⁵ s^-1 and react with O₂ to form CF₃C(O)O₂ radicals with a rate constant of (7.3 ± 1.1) × 10^-13 cm³ molecule^-1 s^-1. In 1 atm of N₂ at 296 ± 2 K, the rate constant ratio k(CF₃CO + O₂ → CF₃C(O)O₂)/k(CF₃CO → CF₃ + CO) = (7.4 ± 0.6) × 10^-18 cm³ molecule^-1. Reaction with O₂ accounts for 99.5% of the loss of CF₃CO radicals in the atmosphere. The ultraviolet absorption spectrum of CF₃C(O)O₂ radicals has been studied over the wavelength range 220-300 nm, and at 230 nm, σ_CF3C(O)O2 = (3.78 ± 0.43) × 10^-18 cm² molecule^-1. Monitoring the rate of NO₂ formation at 400 nm allowed a lower limit of k₄ > 9.9 × 10^-12 cm³ molecule^-1 s^-1 to be derived for the rate constant of the reaction of CF₃C(O)O₂ radicals with NO. Reaction of CF₃C(O)O₂ radicals with NO produces the alkoxy radical CF₃C(O)O, which undergoes C-C bond scission rapidly with a rate greater than 6 × 10⁴ s^-1. Results are discussed with respect to the atmospheric chemistry of CF₃CO_x radicals. As part of the present work, a rate constant k₆ = (2.3 ± 0.4) × 10^-11 cm³ molecule^-1 s^-1 was determined for the reaction of F atoms with CF₃CHO.