X irradiation, at room temperature, of a single crystal of Ph₃P⁺CH₂SCH₃Cl^- produces two radical species which are identified from an analysis of their ESR and ENDOR spectra. The resulting ³¹P, ¹H(CH) and ¹H(CH₃) hyperfine coupling tensors show that one of these radicals is Ph₃P⁺CHSCH₃. The g tensor and the ¹H and ³¹P coupling tensors obtained for the second radical lead to the identification of Ph₃P⁺CH₂S˙S. It is shown that, for this sulfur centered radical, the C-P bond makes an angle of ~ 127° with the sulfur π* orbital containing the unpaired electron.