Methods are being sought to better characterize and identify these azo dyes and their transformation products, in order to predict their transport, transformation and potential fate and effects in receiving waters. Eight monosulfonated and disulfonated azo dyes were analyzed using liquid secondary ion mass spectrometry/tandem mass spectrometry, in the negative ion mode, under low-energy conditions (110-150 eV). Many structurally characteristic fragment ions were obtained, several of which have not been reported previously using other mass spectrometric techniques. Among the structurally important ions observed were those due to loss of SO2, SO3 and various aromatic substituents, such as NO2 and NHCOCH3. Losses of N2 also were proposed. In addition, product ions due to cleavage at the azo linkage were observed, and also SO3(-) and HSO3(-) ions. Several of the azo cleavage product ions detected did not contain sulfonate groups. Possible pathways for the formation of product ions are proposed. The structural information obtained should help to better characterize and identify sulfonated azo dyes in the future.