The threshold photoelectron spectra (TPES) and ion dissociation breakdown curves for trifluoroacetic acid (TFA) and trifluoroacetic anhydride (TFAN) were measured by imaging photoelectron photoion coincidence spectroscopy employing both effusive room-temperature samples and samples introduced in a seeded molecular beam. The fine structure in the breakdown diagram of TFA mirroring the vibrational progression in the TPES suggests that direct ionization to the (X) over tilde (+) state leads to parent ions with a lower "effective temperature" than nonresonant ionization in between the vibrational progression. Composite W1U, CBS-QB3, CBS-APNO, G3, and G4 calculations yielded an average ionization energy (IE) of 11.69 +/- 0.06 eV, consistent with the experimental value of 11.64 +/- 0.01 eV, based on Franck-Condon modeling of the TPES. The measured 0 K appearance energies (AE(0K)) for the reaction forming CO2H+ + CF3 from TFA were 11.92 for effusive data and 11.94 +/- 0.01 eV for molecular beam data, consistent with the calculated composite method 0 K reaction energy of 11.95 +/- 0.08 eV. Together with the 0 K heats of formation (Delta H-f(0K)) of CO2H+ and CF3, this yields a Delta H-f(0K) of neutral TFA of -1016.6 +/- 1.5 kJ mol(-1) (-1028.3 +/- 1.5 kJ mol(-1) at 298 K). TFAN did not exhibit a molecular ion at room-temperature conditions, but a small signal was observed when rovibrationally cold species were probed in a molecular beam. The two observed dissociation channels were CF3C(O)OC(O)(+) + CF3 and the dominant, sequential reaction CF3CO+ + CF3 + CO2. Calculations revealed a low-energy isomer of ionized TFAN, incorporating the three moieties CF3CO+, CF3, and CO2 joined in a noncovalent complex, mediating its unimolecular dissociation.