Polyvinyl alcohol/ZnO (PVA/ZnO) hybrid nanofibers were prepared by the electrospinning technique. The structural and spectral information of the nanofibers was characterized by scanning electron microscopy, x-ray diffraction, Fourier transform infrared spectroscopy, differential scanning calorimetry, resonant Raman, and photoluminescence (PL). The results indicate that ZnO were successfully embedded in the one-dimensional hybrid fibers via chemical interactions between ZnO and PVA. PL results show the PVA/ZnO nanofibers have an intense white-light emission, which originates from the simultaneous emission of three bands covering from the UV to visible range. A possible PL mechanism was proposed accordingly.