The UV photoelectron spectrum of CF(3)CHF(2) has been recorded and assigned using EOM-CCSD calculations. For the first band, the adiabatic ionization energy (AIE) and vertical ionization energy (VIE) have been measured as (12.71 +/- 0.05) and (13.76 +/- 0.02) eV, respectively. The measured AIE is higher than the recommended value from state-of-the-art ab initio calculations of (12.26 +/- 0.02) eV because of a large geometry change on ionization, mainly arising from a significant increase in the C-C bond length, which results in poor Franck-Condon factors in the adiabatic region. The experimental VIE also shows poor agreement with the computed value of 14.05 +/- 0.06 eV because, in the higher energy region of the first photoelectron band, dissociation of CF(3)CHF(2)(+) to CHF(2)(+) + CF(3) occurs. This has a calculated thermodynamic onset of (12.89 +/- 0.20) eV. Recommendations are made for the heats of formation, DeltaH(f,298)(slashed circle), of CF(3)CHF(2) and CF(3)CHF(2)(+), based on the results of the ab initio calculations. Pyrolysis of flowing CF(3)CHF(2) diluted in argon shows evidence of production of C(2)F(4) and HF at lower temperatures and CF(2) and CF(3)H at higher temperatures. The relative temperature dependence of the observed photoelectron bands associated with these molecules is interpreted in terms of two decomposition reactions of CF(3)CHF(2) as well as the reaction C(2)F(4) --> 2CF(2).