We report the fabrication of composite nanofiber mats of poly(lactic acid)/poly(glycidyl methacrylate)/fluorescein [(PLA)/(PGMA)/fluorescein] hybrids via an electrospinning route. Initially, PGMA with low molecular weight was synthesized by free radical polymerization. Then the fluorescent electrospun nanofiber mats were fabricated from the blending of fluorescein and PLA/PGMA in methylene chloride/N,N'-dimethylformamide solution. The influences of the reagent proportions and electrospinning parameters on the morphology of the nanofibers were thoroughly investigated. The as-prepared electrospun fibrous mats showed favorable fluorescence, which meant that the mats could be used in fingerprint recognition and silk-screen printing, as well as amine analysis. This facile method may find potential applications in forensic investigation, reactive microchips and medical diagnostics.