AbstractThe kinetics of thermal decomposition of ethyl, isopropyl, andt‐butyl trifluoroacetates have been studied in the gas phase. In each case initial decomposition follows the normal ester route to give an olefin and trifluoroacetic acid, and elimination of hydrogen fluoride does not occur. However, trifluoroacetic acid is thermally unstable at ethyl and isopropyl ester decomposition temperatures, and further products result, including those from the difluorocarbene produced by decomposing trifluoroacetic acid. Placing a CF3group at an ester's γ carbon increases the polarity of its transition state and decreases its thermal stability. The activation energies of the ethyl and isopropyl esters are lowered by 3.8 and 4.7 kcal/mol compared to the corresponding acetates, and the primary decomposition kinetics, which are homogeneous and of the first order, are expressed byα‐Methylation enhances the reactivity of the trifluoroacetates, and thet‐butyl ester, the transition state for which is sufficiently polar for heterogeneous decomposition to occur, shows signs of thermal instability at room temperature. The equilibriumwas also investigated and gave ΔH° = +13,580 cal/mol and ΔS° = +31.07 gibbs/mol in the forward direction. The results obtained extend and support the known structure–rate correlations in the gas‐phase elimin