Sulfuryl diazide, O2S(N-3)(2), previously described as an "exceedingly explosive" compound, has been isolated and characterized by IR (Ar matrix, gas) and Raman (solid) spectroscopy, and its structure has been determined by X-ray crystallography. It has a melting point of -15 degrees C and can be handled in small quantities in gas, liquid, and solid states. Vibrational spectroscopic studies suggest the presence of only one conformer in both gas and solid states, and the X-ray crystallography revealed an anti conformation of the two azido groups with respect to the NSN plane. Calculations predict the anti (C-2) conformer to be 6.6 kJ mol(-1) lower in energy than the syn (C-s) one at the CBS-QB3 level of theory. The related chlorosulfuryl azide, ClSO2N3, has also been prepared and characterized by IR and Raman spectroscopy.