AbstractA previously uncharacterized atmospheric source of the persistent greenhouse gas tetrafluoromethane, CF4, has been identified in the UV photolysis of trifluoroacetyl fluoride, CF3C(O)F, which is a degradation product of several halocarbons currently present in the atmosphere. CF4 quantum yields in the photolysis of CF3C(O)F were measured at 193, 214, 228, and 248 nm, wavelengths relevant to stratospheric photolysis, to be (75.3 ± 1) × 10−4, (23.7 ± 0.4) × 10−4, (6.6 ± 0.2) × 10−4, and ≤0.4 × 10−4, respectively. A 2‐D atmospheric model was used to estimate the contribution of the photochemical source to the global CF4 budget. The atmospheric photochemical production of CF4 from CF3CH2F (HFC‐134a), CF3CHFCl (HCFC‐124), and CF3CCl2F (CFC‐114a) per molecule emitted was calculated to be (1–2.5) × 10−5, 1.0 × 10−4, and 2.8 × 10−3, respectively. Although CF4 photochemical production was found to be relatively minor at the present time, the identified mechanism demonstrates that long‐lived products with potential climate impacts can be formed from the atmospheric breakdown of shorter‐lived source gases.