In this paper, the surface morphologies of polyvinyl alcohol/milk nanofibers produced via electrospinning technique were investigated. The electrospinning process was performed at various processing parameters (flow rate, applied voltage) and different polyvinyl acetate to milk ratios (100/0, 90/10, 80/20, 70/30, and 60/40). The scanning electron microscopy and Image J software were used to characterize the surface morphologies, especially the diameter distribution of electro spun nanofibers. The results of scanning electron microscopy show that the diameter of polyvinyl acetate/milk nanofibers increases with the increase of the spinning speed and spinning voltage but decreases with the increase of the weight percentage of milk in the spinning solution. The potential applications of this bicomponent nanofibers are numerous and diverse. The research results in present paper can contribute to better control of the electrospinning process and thus expanding the applicabilities, such as dressings for wound healing in sports.