Diphenylsulfene (5) and diphenyl-alpha-sultine 6 were generated in cryogenic matrices by three independent routes : (i) the thermal reaction of diphenylcarbene (8) and SO2, (ii) the photochemically induced hetero Wolff rearrangement of sulfonylcarbene 11, and (iii) oxygen transfer from ozone to diphenylsulfine 16. Isotopic labeling with C-13 and O-18 allows for the assignment of several characteristic IR vibrations of 5. Irradiation with lambda > 375 nm results in the rearrangement of 5 to 6, which is the first alpha-sultine that has been characterized spectroscopically. The final Product on UV irradiation of 6 is benzophenone (9) and sulfur monoxide.