The effect of overtone-induced chemistry on the atmospheric fate of trifluoroacetic acid has been investigated. We report the absolute absorption intensities for the,upsilon(OH) = 3,4, and 5 overtone transitions as well as an ab initio calculation of the energetics of the dissociation pathways. Calculations at the MP2 level give the lowest dissociation barrier as 50.3 kcal mol(-1) for the elimination of HF. Integrated cross sections for upsilon(OH) = 3, 4, and 5 are 2.70 x 10(-20), 1.68 x 10(-21), and 1.5 x 10(-22) cm(2) molecule(-1) cm(-1), respectively. Dissociation may proceed after absorption into v = 5 or 6, giving an upper limit to the photodissociation rate constants of 3.7 x 10-9 s(-1) or 2.5 x 10(-10) s(-1), respectively. These correspond to a tropospheric lifetime of between 8 and 127 years. The overtone-driven photodissociation is more important than the ultraviolet photodissociation in the troposphere but is insignificant in comparison to wet deposition and the reaction with OH radicals.