Uniform and bead-free polyvinyl alcohol (PVA) and its nanocomposite fibers filled with different loadings of CdSe@ZnS quantum dots (QDs) were prepared by the electrospinning process. The incorporation of QDs into PVA solution lowered the viscosity of the system. The electrospinning parameters, including applied voltage, feed rate, and working distance were optimized to prepare high quality nanocomposite fibers. Increasing the voltage from 20 to 25kV, the average diameter of PVA fibers reduced from ca. 284 to 164nm (42.5% decrease) and the average diameter of PVA/QDs nanocomposite fibers decreased from ca. 365 to 240nm (34.2% decrease). The PVA/QDs (5.0wt%) nanocomposite fibers were examined under a fluorescent microscopy. The thermal stability was investigated by both thermogravimetric analysis and differential scanning calorimetry. Fourier transform infrared spectroscopy was utilized to characterize the functionality of the fibers and to investigate the interaction between PVA and inorganic additions. Unique fluorescent phenomenon was observed in the PVA fibers after incorporation of small amount of QDs.