A series of La2W2O9: xEu(3+) (x = 2, 4, 6, 8, and 10 mol%) nanofibers have been synthesized by electrospinning method and characterized by PXRD diffraction, SEM, and EDS. The influences of different Eu3+ concentrations and calcination temperatures on the crystallinity of La2W2O9: Eu3+ nanofibers have been investigated by PXRD diffraction. The luminescence properties of La2W2O9: Eu3+ nanofibers have been discussed in detail, and it indicated that La2W2O9: 8 mol% Eu3+ had the highest fluorescence intensity and the longest lifetime, which emphasized a potential application to white light LED phosphor and biological imaging.