We reported the preparation and characterization of the poly(vinyl alcohol) (PVA)/BaSO4 hybrid nanofibers prepared by normal and ultrasonic electrospinning, respectively. Compared to normal electrospinning, BaSO4 particles in the resultant PVA/BaSO4 hybrid nanofibers prepared by ultrasonic electrospinning were well-dispersed without severe agglomerations, as confirmed by scanning electron microscopy (SEM) analysis. X-ray diffraction (XRD) analysis indicated that typical crystalline peaks of PVA and BaSO4 particles were dramatically decreased by ultrasonication during electrospinning. Moreover, the size of BaSO4 aggregates became smaller.