We report on the preparation and characterizations of multifunctional baicalein blended poly(vinyl alcohol) (PVA) composite nanofibers via electrospinning process. In order to improve the biocompatibility properties, baicalein was blended in to PVA to prepare composite nanofibers. The morphology, structure and thermal properties of the PVA/baicalein composite nanofibers were analyzed by using scanning electron microscopy (SEM), X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, Raman spectroscopy and thermogravimetry (TGA) analysis. SEM images revealed that the composite nanofibers were well-oriented and had good incorporation of baicalein. FT-IR results indicated that the various bonding groups of PVA/baicalein composite nanofibers with stable structure. TGA analysis revealed that the onset degradation temperature was decreased with increasing baicalein content in the composite nanofibers. Ultraviolet (UV) light blocking efficiency was enhanced with increasing baicalein concentration in the composite nanofibers as observed by UV-vis diffuse reflectance spectroscopy. Further, the bactericidal activity of PVA/baicalein composite nanofibers was also investigated. These results indicated that the PVA blended baicalein composite nanofibers can be utilized as promising candidate materials for many technological applications. © 2011 Elsevier B.V.