Y(2)O(3): Eu(3+) nanofibers with the average diameter of ~300 nm were in situ fabricated by electrospinning. X-ray diffraction (XRD) pattern confirmed that the Y(2)O(3): Eu(3+) nanofibers were composed of pure body-centered cubic (bcc) Y(2)O(3) phase. High-resolution transmission electron microscopy (HRTEM) results indicated that Y(2)O(3): Eu(3+) nanofibers were constituted of nonspherical crystalline grains, and these crystalline grains were orderly arranged along the axial direction of single nanofiber. These Y(2)O(3): Eu(3+) nanofibers showed a partially polarized photoluminescence (PL). The arrangement of crystalline grains and the mismatch of dielectric constant between Y(2)O(3): Eu(3+) nanofiber and its environment probably contributed together to the polarized PL from Y(2)O(3): Eu(3+) nanofiber.