A new kind of fluorescence probe, a fluorophore-labeled anionic surfactant, sodium 12-(N-dansyl)aminododecanate (12-DAN-ADA), was designed and synthesized. The applications of 12-DAN-ADA as a fluorescence probe in molecular assemblies, especially in the transitions between micelles and vesicles, were investigated systematically. It was found that 12-DAN-ADA can efficiently differentiate the two different aggregate types (shapes) in mixed cationic and anionic surfactant systems and double-chain cationic surfactant systems. Experimental results showed that the fluorescence anisotropy of 12-DAN-ADA increased sharply, the emission maxima became blue-shifted, and the fluorescence lifetime rose notably when the aggregates transformed from micelles to vesicles in mixed cationic and anionic surfactant systems. The fluorescence anisotropy can also distinguish different aggregate types in single-component double-chain cationic surfactant systems. Further studies demonstrated that 12-DAN-ADA is a more useful probe of transitions between micelles and vesicles than commonly used fluorescence probes, such as pyrene and 1,6-diphenyl-1,3,5-hexatriene (DPH). (c) 2008 Elsevier Inc. All rights reserved.