The dissociative photoionization of CH3SSCH3 has been investigated in the photon energy range of similar to 8-25 eV with a molecular beam/photoionization mass spectrometry/threshold photoelectron spectrometry system using synchrotron radiation as an ionization source. For dissociation above photon energy of 11.5 eV, six fragment ions of CH3+, C2H3+, SH3+, HCS+, S-2(+), and CH2S2+ were reported for the first time. The photoionization efficiency spectra for the parent ion and for 12 observed fragment ions, CH3+, C2H3+, SH3+, HCS+, CH2S+, CH2SH+, CH3SH+, CH3SH2+, CH3SH2+, S-2(+), CH2S2+, and CH2S2H+, were measured; their branching ratios as a function of photon energy were derived. Ionization energy of 8.20 +/- 0.04 eV for CH3SSCH3 and the appearance energy for each fragment ion were determined from the onsets of the photoionization efficiency spectra. Based on the appearance energy and existing thermochemical data, plausible structures of the fragment ions and their neutral counterparts are proposed. Fragmentation mechanisms that involve H migration and structural rearrangement in the dissociative photoionization processes are discussed.