Abstract A final decision between the 2-and 3-oxide structure of the thermally or photo-chemically accessible monoxides of 1,2,3-thiadiazoles is given with the aid of an X-ray analysis of 4-phenyl-1,2,3-thiadiazole-3-oxide. The compound crystallizes in the ortho-rhombic space group Pbca, Z = 8, with a = 7.598(6), b= 18.865(5) and c= 11.225(6) Å. The structure was solved by the heavy atom method and refined to R = 0.042 for 1643 independent reflections. The heterocyclic ring is planar within experimental error and the bond distances S-C and S-N are rather short. In the crystal the molecules are linked by an unusual short contact distance between sulphur and oxygen (2.75 Å).