The threshold-ion-pair-production (TIPP) spectra of H2S and D2S have been recorded in the vicinity of the and thresholds using a tunable vacuum-ultraviolet laser and cold molecular samples () in supersonic expansions. The ion-pair-production signal was found to be much stronger at the thresholds than at the thresholds. From the rotational structure of the spectra, the dominant photodissociation partial waves are determined to be those with , which indicates that dissociative Rydberg states of H2S with a linear ion core are involved in the formation of the ion-pair states. The H + +SH − ion-pair-dissociation threshold energy we derive for H2S is in excellent agreement with the value reported in an earlier TIPP-spectroscopic investigation by Shiell et al. [J. Phys. Chem. A 104 (19), 4339–4342 (2000)]. From our new values of the ion-pair-dissociation thresholds, we determine improved bond-dissociation energies and of and , respectively, where the numbers in parentheses represent an uncertainty of in units of the last digit.