This paper describes a procedure based on electrospinning for generating europium-doped yttrium vanadate (YVO4:Eu3+) nanofibers with diameters ranging from 30 to 50 nm. The YVO4:Eu3+ nanofibers were obtained through calcining precursory nanofibers, which were prepared through the electrospinning method. Suitable electrospinning parameters, such as concentration of PVP in solution, spinneret tip-to-collector plate distance (TCD), and applied voltage between spinneret and collector plate, are used to obtain thinner and more uniform precursory nanofibers of YVO4:Eu3+, which is important for preparing smaller diameter pure YVO4:Eu3+ nanofibers. The luminescent properties of the YVO4:Eu3+ nanofibers including excitation and emission spectra and fluorescence lifetime were studied. The excitation spectrum shows a broad band extending from 200 to 350 nm, which corresponds to the strong vanadate absorption in YVO4:Eu3+. The emission spectrum is dominated by the red 5D0 --> 7F2 hypersensitive transition of Eu3+. The fluorescence lifetime of Eu3+ 5D0 --> 7F2 (619 nm) is determined to be 493 micros at room temperature, which is basically in accordance with that in the bulk (521 micros).