One hemicyanine dye, DHEASPBr-C2, has been synthesized in this paper and incorporated by doping to Polyvinyl Alcohol (PVA) to prepare the fluorescent nanofiber webs. SEM morphology and fluorescent properties of the electrospun webs were tested. Results showed that it is feasible to develop fluorescent orange nano-fibre webs from those incorporating solutions using electrospinning process (ESP) at room temperature. When measuring fibres selected from each electronspun webs in SEM images, the fibres diameters changed between 200 nm and 400 nm with the change of electrospinning technological parameters. The reflectance spectra of the electrospun webs showed that there are obvious sorption spectra in the range 380-550 nm and emission spectra in the range 560-700 nm, while the single-photon fluorescent emission spectra showed obvious fluorescent effect.