In this work, the 254 nm photolysis of CF₃CHO was investigated using a 101 L quartz chamber coupled with FTIR detection. The overall quantum yield was determined as (0.52 ± 0.07) at 700 Torr, independent of diluent gas. Photolysis in 700 Torr N₂ and in the presence of NO yields (26 ± 3) % CF₃H and (73 ± 6) % CF₃NO. In 700 Torr of air or oxygen, products identified include CF₃H, COF₂, CF₃OH, CF₃O₂CF₃ and CF₃O₃CF₃. In the presence of NO in 700 Torr of air or O₂, alkoxy- and peroxy-nitrates were also quantified. A full carbon balance for the fluorine-bearing carbon was achieved. The photolytic channel quantum yields were established: Φ(CF₃H + CO) = (0.16 ± 0.02) and Φ(CF₃ + HCO) = (0.36 ± 0.07) at 700 Torr total pressure. This is the first large chamber study of the stratospheric photolysis of CF₃CHO. The quantum yields measured here are lower than those reported previously and show a different relative importance associated with the photolysis channels. Atmospheric photolysis coefficients of CF₃CHO were modeled giving an estimate for the average atmospheric lifetime for CF₃CHO of 13 ± 4 days (at 5 km altitude, tropics). Based on the present work, photolytic production of CF₃H, which is a strong greenhouse gas, can occur at stratospheric altitudes above 30–40 km. This has implications for the environmental impact of CF₃CHO generated as an oxidation product in the higher atmosphere from long-lived chlorofluorocarbon-replacement compounds. However, the majority of CF₃CHO will undergo photochemical degradation in the lower troposphere. Hence, photochemical degradation of CF₃CHO will make a negligible contribution to the atmospheric burden of CF₃H.