Zinc oxide/polyvinylpyrrolidone (ZnO/PVP) nanocomposite fibers with enhanced structural, morphological and optical properties were purposefully tailored using electrospinning technique. Meanwhile, ZnO nanoparticles (NPs),with particle size of ~50 nm, were synthesized using a co-precipitation method. The nanocomposite fibers were prepared by an electrospun solution of PVP containing ZnO NPs of 2, 4, 6 and 8 wt%. Evidently, the morphological, thermal and optical properties of the ZnO/PVP nanocomposite fibers were enhanced by dispersing ZnO NPs into PVP fibers. Typically, controlling the ZnO NPs content and their dispersibility (0–8 wt%) into PVP fibers result in improved the thermal stability (an increase of onset decomposition temperature by ~120 °C above pure PVP fibers) as well as the UV–Vis protection (reduction in UV transmission by 70%) and the photoluminescence properties (a sharp UV emission around 380 nm) Overall, based on the enhanced properties, the PVP/ZnO nanocomposite fibers can be considered a promise material in optoelectronic sensors and UV photoconductor.