We report on the preparation and characterizations of Scutellariae Radix (SR) blended poly(vinyl alcohol) (PVA)/blocked isocyanate prepolymer (BIP) composite nanofibers via electrospinning process. In order to improve the biocompatibility properties, SR biological macromolecules were blended in PVA/BIP composite nanofibers. SEM images revealed that the composite nanofibers were well-oriented and had good incorporation of SR. Ultraviolet (UV) absorbance spectra revealed that the maximum measured absorbance intensities were linearly increased with increasing SR in the composite nanofibers. TEM images revealed a peculiar morphology by the additive SR. This additive SR possesses a lower molecular component which was exhibited at the outside of the nanofibers structure due to strong applied electric field during electrospinning process. These results indicated that the PVA/BIP blended SR composite nanofibers might be utilized for many biomedical applications including control release and wound dressing.