Photodissociation of fluorine-substituted benzenes, including 1,3-difluorobenzene, 1,2,4-trifluorobenzene, 1,2,4,5-tetrafluorobenzene, and pentafluorobenzene, at 193 nm, under collision-free conditions has been studied in separate experiments using multimass ion imaging techniques. HF elimination was found to be the major dissociation channel for all of these molecules. Small amounts of photofragments of C6H3F2 and C6H2F3 from 1,3-difluorobenzene and 1,2,4-trifluorobenzene, respectively, were also observed. They correspond to the minor dissociation channel of hydrogen elimination. Dissociation rates and fragment translational energy distributions obtained from experimental measurements suggest that HF and hydrogen elimination reactions occur in the ground electronic state. The potential energy surface obtained from ab initio calculations indicates that the four-center reaction in the ground electronic state is the major dissociation mechanism for the HF eliminations. A comparison with the RRKM calculation has been made.