Picosecond transient absorption spectroscopy was utilized to study the recombination dynamics of triplet sulfur radical pairs. A disulfide, bis (p-benzoylphenyl) disulfide (BpSSBp), was designed to selectively produce triplet thiyl radicalpairs by means of internal triplet energy transfer. Thus, irradiation of bis (p-benzoylphenyl) disulfide (BpSSBp) in Tetralin (355 nm, 17 ps) followed by instantaneous singlet—triplet interconversion of the photoexcited benzoyl group leads to rapid intramolecular energy transfer and S—S bond scission. Greater than 50% of the photochemically generated (presumably triplet) radicalpairs were found to recombine in competition with cage escape. Benzoyl substitution of phenyl disulfide is expected to cause intersystem crossing (ISC) from the singlet excited state to the triplet state to occur before singlet S—S bond scission can occur. However, benzoyl substitution is not expected to perturb the orbital degeneracy on the thiyl radical that has been suggested to be responsible for the strong spin—orbitcoupling mechanism and fastISC of sulfur-centered radical pairs in micellar solutions. Thus, this study provides the first directobservation of fast ISC (> 100 ps) of sulfur-centered radical pairs in organic solvents.