YF3:Tb3+ hollow nanofibers were successfully fabricated via fluorination of the relevant Y2O3:Tb3+ hollow nanofibers which were obtained by calcining the electrospun PVP/[Y(NO3)(3) + Tb(NO3)(3)] composite nanofibers. The morphology and properties of the products were investigated in detail by X-ray diffraction, scanning electron microscope, transmission electron microscope, and fluorescence spectrometer. YF3:Tb3+ hollow nanofibers were pure orthorhombic phase with space group Pnma and were hollow-centered structure with the mean diameter of 148 +/- A 23 nm. Fluorescence emission peaks of Tb3+ in the YF3:Tb3+ hollow nanofibers were observed and assigned to the energy levels transitions of D-5(4) -> F-7(J) (J = 6, 5, 4, 3) (490, 543, 588, and 620 nm) of Tb3+ ions, and the D-5(4) -> F-7(5) hypersensitive transition at 543 nm was the dominant emission peak. Moreover, the emitting colors of YF3:Tb3+ hollow nanofibers were located in the green region in CIE chromaticity coordinates diagram. The luminescent intensity of YF3:Tb3+ hollow nanofibers was increased remarkably with the increasing doping concentration of Tb3+ ions and reached a maximum at 7 mol% of Tb3+. The possible formation mechanism of YF3:Tb3+ hollow nanofibers was also discussed. This preparation technique could be applied to prepare other rare earth fluoride hollow nanofibers.