Europium-doped yttrium orthovanadate/polyethylene oxide nanofibers were fabricated by firstly, synthesizing crystalline YVO4:Eu3+ nanoparticles using an aqueous precipitation method followed by electrospinning of PEO/YVO4:Eu3+ polymer composites. X-ray diffraction patterns showed that the nanoparticles exhibited well-defined peaks that were indexed as the tetragonal phase of YVO4. No additional peaks of other phases were observed indicating that Eu3+ ions were effectively built into the YVO4 host lattice. The photoluminescence spectra for the nanofibers showed peaks at 593, 615, 650, and 698nm which was ascribed to the 5D0-7F1, 5D0-7F2, 5D0-7F3 and 5D0-7F4 transitions of Eu3+. Due to an efficient energy transfer from vanadate groups to Eu3+, the composite nanofibers showed a strong red emission under ultraviolet excitation characteristic of the red luminescence of the europium ion. The results demonstrate that this synthetic approach could prove to be viable for the fabrication of rare earth/polymer composite nanofibers intended for luminescent device applications.