The preparation of 1,3-dinitrophenoxathiin represents the first reported synthesis of the phenoxathiin ring system. Based on known relative nucleophilicities either an unprecedented reversal of nucleophilicities or the occurrence of a Smiles Rearrangement would be required to account for the reported substituent locations. The re-examination of this synthesis with confirmation of actual substituent locations by13C-nmr and the correction of the original literature is described.