The NIST tandem mass spectral library (2020 version) includes over 800 aromatic sulfonamides. In negative mode, upon collisional activation most benzenesulfonamides lose a neutral SO2 molecule leading to an anilide anion (C6H5NH-, m/z 92). However, for deprotonated N-benzoyl aromatic sulfonamides, the phenoxide ion (C6H5O-, m/z 93.0343) is the principal product ion. A variety of N-acylbenzenesulfonamide derivatives were also found to overwhelmingly produce the phenoxide ion as the most intense product ion. A mechanism is proposed in which, at low energy, a carbonyl oxygen atom (C═O) is transferred to a benzene ring, known as a Smiles-type rearrangement (the amide oxygen atom attacks the arylsulfonyl group at the ipso position), in parallel and determining the reaction at high energy a nitrogen-oxygen rearrangement mechanism leads to the formation of the phenoxide ion. Tandem mass spectra of deprotonated N-benzoyl-18O-benzenesulfonamide and N-thiobenzoyl-p-toluenesulfonamide confirmed the rearrangement since base peaks at m/z 95.0384 and 123.0270 which correspond to an 18O phenoxide ion ([C6H518O]-) and a 4-methylbenzenethiolate anion ([CH3C6H4S]-) were observed, respectively. The parallel mechanism is supported by the strong correlation between the observed product ion intensities and the corresponding activation energies obtained by Density Functional Theory calculations. This is an example of a relatively simple ion with a complex path to fragmentation, being a cautionary tale for indiscriminate use of in silico spectra in place of actual measurement.