H(D) Rydberg atom photofragment translational spectroscopy has been used to investigate the dynamics of H(D) atom loss C6H5SH(C6H5SD) following excitation at many wavelengths lambda(phot) in the range of 225-290 nm. The C6H5S cofragments are formed in both their ground ((XB1)-B-2) and first excited (B-2(2)) electronic states, in a distribution of vibrational levels that spreads and shifts to higher internal energies as lambda(phot) is reduced. Excitation at lambda(phot) > 275 nm populates levels of the first (1)pi pi* state, which decay by tunnelling to the dissociative (1)pi sigma* state potential energy surface (PES). S-H torsional motion is identified as a coupling mode facilitating population transfer at the conical intersection (CI) between the diabatic (1)pi pi* and (1)pi sigma* PESs. At shorter lambda(phot), the (1)pi sigma* state is deduced to be populated either directly or by efficient vibronic coupling from higher (1)pi pi* Flux evolving on the (1)pi sigma* PES samples a second Cl, at longer RS-H, between the diabatic (1)pi sigma* and ground ((1)pi pi) PESs, where the electronic branching between ground and excited state C6H5S fragments is determined. The C6H5S((XB1)-B-2) and C6H5S (2 B,) products are deduced to be formed in levels with, respectively, a' and a" vibrational symmetry-behavior that reflects both Franck-Condon effects (both in the initial photoexcitation step and in the subsequent in-plane forces acting during dissociation) and the effects of the out-of-plane coupling mode(s), v(11) and V-16a, at the (1)pi sigma*/(1)pi pi. The vibrational state assignments enabled by the high-energy resolution of the present data allow new and improved estimations of the bond dissociation energies, D-0(C6H5S-H) <= 28030 +/- 100 cm(-1) and D-0(C6H5S-D) <= 28610 +/- 100 cm(-1), and of the energy separation between the (XB1)-B-2 and B-2(2) states of the C6H5S radical, T-00 = 2800 +/- 40 cm(-1). Similarities, and differences, between the measured energy disposals accompanying UV photoinduced X-H (X = S, O) bond fission in thiophenol and phenol are discussed.