Abstract: Photofragmentation of CH_3SSCH_3 at 248nm was studied by using rotatable pulsed molecular beam crossed with excimer laser beam. TOF spectra of the photofragments were measured at eight different lab angles. The energy partitioning between the internal and translational freedoms in CH_3S fragments showed that the dissociation of S—S bond in CH_3SSCH_3 is consistent with impulsive dynamic model. The S—S bond energy in CH_3SSCH_3 was estimated to be 263±11 kJ mol~(-1) based on the maximum translational energy release in CH_3S fragments. The fact that the C—S bond dissociation at 248 nm was not observed in this work may indicate the intramolecular energy transfer is not fast enough comparing with S—S bond scission and suggest that the bond angle between S—S and C—S bond should be close to 90°, instead of linear structure of CSSC frame. The observation of the wide peak in TOF spectra of CH_3S fragments was explained due to the photodissociation of dimer (CH_3SSCH_3)_2, which was formaed in the supersonic molecular beam.