The threshold photoelectron (TPE) spectrum of SF 6 has been recorded over the photon energy range 25-140 eV using synchrotron radiation and a penetrating-field electron spectrometer. In addition, the photo-double ionization spectrum of SF 6 has been obtained over the energy range 30.7-49.3 eV using the threshold photoelectrons coincidence technique. The TPE spectrum in the inner-valence ionization region is found to be significantly different to the conventional photoelectron spectrum in the same binding energy region. Indirect autoionization of neutral Rydberg and shape-resonance states of SF 6 dominate the formation of the TPE spectrum. Innervalence SF + 6 ion states appear to play a major role in the formation of the SF 2+ 6 ion states. The onset of double ionization in SF 6 was found to occur at 31.98 ± 0.02 eV.