The luminescent europium complex [Eu(TFI)(3)(Phen)]center dot CHCl3 (TFI = 2-(2,2,2-trifluoroethyl)-1-indone, Phen = 1,10-phenanthroline) was incorporated into poly(vinylpyrrolidone) (PVP) matrixes and electrospun into nanofibers. The effect of [Eu(TFI)(3)(Phen)]center dot CHCl3 on the morphology and luminescence of composite nanofibers has been studied. FT-IR and TGA analyses of the composite nanofibers have been conducted and discussed. Further, the Judd-Ofelt theory is employed to study the effect of the dispersion of [Eu(TFI)(3)(Phen)]center dot CHCl3 and the interactions between the [Eu(TFI)(3)(Phen)]center dot CHCl3 molecules and neighboring chain segments of PVP. The results suggest that PVP led to the increased polarization degree of Eu3+ ions and significantly enhanced the electronic dipole-allowed transitions of Eu3+ ions, resulting in the enhancement of luminescent efficiency.