The dissociative photoionization of gaseous CH3SCN has been investigated at the S 2p core level using time-of-flight mass spectrometry and synchrotron radiation. The total ion yield spectrum could be successfully assigned by comparison with available data from electron energy loss spectra. The relative abundances of the ionic fragments and their kinetic energy release values were obtained from both PEPICO (photoelectron photoion coincidence) and PEPIPICO (photoelectron photoion photoion coincidence) spectra. The dynamics of the ionic fragmentation of S 2p excited CH3SCN is dominated by the rupture of both carbon-sulfur bonds. This process may be related with electronic excitations from the ground electronic state to vacant sigma* molecular orbitals.