PVP/［Y(NO3)3+Al(NO3)3+Eu(NO3)3］ composite nanofibers are prepared via electrospinning, and YAlO3:Eu3+ nanofibers are fabricated by calcination of the prepared composite fibers. The samples are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM) and fluorescence spectroscopy. Pure phase YAlO3:Eu3+ nanofibers are obtained by calcination of the relevant composite fibers at 1200 ℃ for 2 h and YAlO3:Eu3+ nanofibers belong to orthorhombic system with space group Pnma. The diameters of fibers analyzed by Shapiro-Wilk method obey normal distribution under the confidence of level 95%. The surfaces of as-prepared composite fibers are smooth with a good aspect ratio, dispersion and uniform size. The diameters of PVP/［Y(NO3)3+Al(NO3)3+Eu(NO3)3］ fibers and YAlO3:Eu3+ nanofibers are (152.9±26.0)nm and (106.7±20.2)nm, respectively. Fluorescence spectra analysis manifests that YAlO3:Eu3+ nanofibers emit the predominant emission peaks at 590 nm and 609 nm under the excitation of 234 nm ultraviolet ray, attributed to the transitions of 5D0→7F1 and 5D0→7F2 energy levels of Eu3+, respectively. The doping concentrations of Eu3+ have no effect on the shape and wavelength of the emission spectra of YAlO3:Eu3+, and the luminescent intensity reaches a maximum at about 5% of Eu3+.