Decomposition of the CF₃CFHO radical formed in the reaction of CF₃CFHO₂ radicals with NO was studied at 296 and 393 K using a pulse radiolysis transient VIS-UV absorption absolute rate technique. At room temperature in 1 atmosphere of SF₆ diluent it was found that the majority (79 ′ 20)% of CF₃CFHO radicals formed in the CF₃CFHO₂ + NO reaction decompose within 3 μs via C - C bond scission. This result is discussed with respect to the current understanding of the atmospheric degradation of HFC-134a. As a part of the present work the rate constant ratio k_CF3CFH+02/k_CFSCFH+NO was determined to be 0.144 ′ 0.029 in one atmosphere of SF₆ diluent at 296 K.