We have investigated the dissociative photoionization of shallow-core excited CCl3SCl by using multicoincidence time-of-flight mass spectrometry and synchrotron radiation in the S 2p and Cl 2p edges, 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 dynamic of the ionic fragmentation of S and Cl 2p excited CCl3SCl has been studied and compared with those of CCl4. Features determined in the present study seem to be relevant aspects for explaining the dissociation of highly chlorinated species under the action of VUV irradiation. The fragmentation pattern shows that chlorine ion (Cl+) is prominently formed upon both S and Cl 2p excitations.