Ion-molecule reactions of CF3O-, CF3O, and CF3OH were studied using the flowing afterglow technique to evaluate the thermochemistry of CF3OH and related compounds. The gas-phase acidity of CF3OH was measured to be Delta(r)H(acid)(o) = 329.8 +/- 2.0 kcal mol(-1) by ion-molecule reaction bracketing. A limit on the electron affinity of the CF3O radical of greater than or equal to 89.2 kcal mol(-1) was also determined. The CF3O-H bond strength derived from these results is 124.7 +/- 3.6 kcal mol(-1), which is consistent with recent ab initio calculations of the heats of formation of CF3O and CF3OH.