Singly distributed YBO3:Eu nanofibers with an average diameter of around 120 nm were fabricated using the electrospinning technique and characterized by scanning electron microscopy, transmission electron microscopy, and X-ray diffraction. The luminescent properties of the YBO3:Eu nanofibers were studied relative to the corresponding bulk material. The location of the charge transfer band in the excitation spectra shows a slight blueshift in the nanofibers compared with the bulk material. In the emission spectra, the ratio of the red emission at 611 nm to the orange emission at 591 nm (R/O value) in the nanofibers increased slightly, in contrast to the bulk, indicating that improved chromaticity can be obtained from YBO3:Eu nanofibers. The high color-rendering index obtained from them implies that these novel luminescent fibers can be used as potential candidates for nanodevices.