The thermal decomposition of 2-H-heptafluoropropane, CF(3)CHFCF(3), at low pressure, heavily diluted in argon, has been studied over the temperature range 600-2000 degrees C using photoelectron spectroscopy. Comparison of the results obtained has been made with results of recent electronic structure calculations of possible decomposition pathways and results of a shock tube study. The most favored reaction thermodynamically, to produce CF(3)CF=CF(2) + HF, is found to be the main decomposition reaction at lower temperatures, 600-900 degrees C. At higher temperatures, 900-1200 degrees C, the decomposition reaction to give C(2)F(4) + CF(3)H was found to become important. No evidence for CF(3)CHFCF(3) --> CF(3)CHF + CF(3), a reaction expected to be important from a shock tube study, performed at much higher pressures, or for CF(3)CHFCF(3) --> CF(3)CF + CF(3)H was obtained, although for the latter reaction it is likely that CF(3)CF converts into C(2)F(4) under the conditions used before photoionization, in the ionization region of the photoelectron spectrometer. At higher temperatures C(3)F(6) decomposes to C(2)F(4) + CF(2), and C(2)F(4) decomposes to CF(2). Ab initio calculations have been performed of the adiabatic and vertical ionization energies of possible primary pyrolysis products to assist assignment of the photoelectron spectra recorded for heated flowing gas samples. A comparison is made between the threshold photoelectron spectrum and the photoelectron spectrum of CF(3)CF=CF(2).