Electrospinning is a simple and cost-effective approach for the production of nanofibers and assemblies with controllable structures. In this work, the pure poly (diallyldimethylammonium chloride) (PDAC) nanofibers with smooth surface and uniform morphology were successfully fabricated by electrospinning. On this basis, fluorescein/PDAC, dibromofluorescein/PDAC, diidofluorescein/PDAC and fluorescein sodium/PDAC composite nanofibers were also fabricated using the same method. The average diameters of the pure PDAC nanofibers increased with the applied field strength and the amount of PDAC in the solutions; and the average diameters ranged from 280 to 450 nm. The morphology of pure PDAC nanofibers has been observed by scanning electron microscopy (SEM) and the photoluminescent properties of fluorescein derivative/PDAC composite nanofibers have been characterized by fluorescence microscopy. (c) 2008 Elsevier Ltd. All rights reserved.