A new luminescent europium(III) bis-beta-diketonate complex, Eu-2(PBT)(3)(NO3)(3) (PBT = 1,1-(pyridine-2,6-diyl)bis (4,4,4-trifluoro-1,3-dione), was incorporated into the poly(methylmethacrylate) (PMMA) matrix and formed nanofibers via electrospinning technology. The different characterization techniques were adopted to reveal the effect of Eu-2(PBT)(3)(NO3)(3) on the spatial structure and optical properties of the nano-composite fibers obtained. The doping enhances the thermal stability and filament-forming properties for a series of PMMA-supported composite nanofibers Eu/PMMA, and in particular, the doping concentrations of 11 wt% also showed more efficient luminescence properties. Furthermore, the Judd-Ofelt theory was applied in this study to explain the effect of the distribution of Eu-2(PBT)(3)(NO3)(3) and the mutual effect of the Eu-2(PBT)(3)(NO3)(3) coordination compound and surrounding fractions of PMMA.