Poly(vinyl alcohol) (PVA) nanofibers containing functional ZnS nanoparticles have been successfully prepared by electrospinning technique. The ZnS/PVA mixture solution for electrospinning was obtained by reacting Zn(Ac)2 with Na2S in the PVA aqueous solution. Scanning electron microscopy (SEM), transmission electron microscopy (TEM), and X-ray diffraction (XRD) analyses revealed that the morphology of the ZnS/PVA nanofibers consists of the dispersion of ZnS nanopaticles with cubic structure in PVA nanofibers. The coordinations between –OH and Zn2+ were characterized by infrared spectroscopy. The photoluminescence spectroscopy studies showed that the ZnS/PVA nanofibers had a strong blue-violet emission band at 450 nm, which may be associated with defect-related emission of the ZnS.