We studied the gas-phase photodissociation of a fully halogenated aromatic molecule,tetrabromothiophene, upon core–shell ionization by using synchrotron radiation and energy-resolvedmultiparticle coincidence spectroscopy. Photodynamics was initiated by the selective soft X-rayionization of three elements – C, S, and Br – leading to the formation of dicationic states by Augerdecay. From a detailed study of photodissociation upon Br 3d ionization, we formulate a generalfragmentation scheme, where dissociation into neutral fragments and a pair of cations prevails, butdicationic species are also produced. We conclude that dicationic tetrabromothiophene typically undergoesdeferred charge separation (with one of the ions being often Br+) that may be followed by secondarydissociation steps, depending on the available internal energy of the parent dication. Observations suggestthat the ejection of neutral bromine atoms as the first step of deferred charge separation is a prevailingfeature in dicationic dissociation, although sometimes in this step the C–Br bonds appear to remain intactand the thiophene ring is broken instead. Ionization-site-specific effects are observed particularly in doublycharged fragments and as large differences in the yields of the intact parent dication. We interpret theseeffects, using first-principles calculations and molecular dynamics simulations of core-hole states, as likelycaused by the geometry changes during the core-hole lifetime.