The simplest N-sulfonylamine HNSO2 has been generated in the gas phase through flash vacuum pyrolysis of methoxysulfonyl azide CH3OS(O)(2)N-3. Its identification was accomplished by combining matrix isolation IR spectroscopy and quantum chemical calculations. Both experimental and theoretical evidence suggest a stepwise decomposition of the azide via the methoxysulfonyl nitrene CH3OS(O)(2)N, observed in the 193 nm laser photolysis of the azide, with concerted fragmentation into CH2O and HNSO2. Upon the 193 nm laser irradiation, HNSO2 isomerizes into the novel N-hydroxysulfinylamine HONSO.