Photolysis of (R-s,S-c)-l-deuterio-2,2-dimethylpropyl p-tolyl sulfoxide provides mainly (S-s,S-c)-1-deuterio -2,2-dimethylpropyl p-tolyl sulfoxide at low conversion, though the other two stereoisomers are formed to smaller extents. Thus, the predominant process leading to sulfur inversion yields only sulfur inversion, without inversion of the adjacent CHD stereogenic center. This is taken as evidence for a mechanism for photochemical epimerization of sulfoxides that does not involve homolytic alpha-cleavage chemistry.