The kinetics of the reaction between fluorine atoms and trifluoroacetic acid has been studied experimentally at T = 258-343 K. The overall reaction rate constant decreases with temperature: k(1)(T) = 1.09 x 10(-12) exp((+1034 K)/T) cm(3) molecule(-1) s(-1). The potential energy surface of the reaction has been studied using quantum chemistry. The results were used in transition state theory calculations of the temperature dependences of the rate constants of the two channels of the reaction. The abstraction channel ultimately producing HF is dominant at the experimental temperatures; the addition-elimination channel producing CF3 and CF(O) OH becomes important above 1000 K. (C) 2011 Elsevier B.V. All rights reserved.