In this work, two kinds of 4, 4-difluoro-4-bora-3a, 4a-diaza-s-indacene (BODIPY) composite nanofibers with excellent emitting properties are reported. These contain 5,5-difluoro-1,3,7,9-tetramethyl-10-phenyl-5H-dipyrrolo[1,2-c:2,1-f][1,3,2]diazaborinin-4-ium-5-uide (DBDP) and 10-(4-(diphenylamino)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-dipyrrolo[1,2-c:2,1-f][1,3,2]diazaborinin-4-ium-5-uide (TBDP). DBDP and TBDP, which were obtained using a one-pot process, were respectively incorporated into the poly(methylmethacrylate) (PMMA) matrix with different concentrations and thus formed two series of BODIPY luminescent nanofibers via electrospinning technology. The composite nanofibers were further characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), thermogravimetric analysis (TGA) and luminescence. The SEM images show that the composite nanofibers have a smooth and uniform surface with a diameter about 0.4 mu m. FT-IR spectra analysis indicates that the BODIPY compounds were successfully doped into the PMMA matrices. The TGA results show that decomposition temperature of BODIPY nanofibers was increased to about 113? and 88? for TBDP and DBDP, respectively, compared with that of BODIPY compounds. Furthermore, the BODIPY nanofibers also exhibit excellent optical fluorescence properties compared with the BODIPY compounds in dichloromethane (BODIPY/DCM) or in a solid state.