Bubble electrospinning exhibits profound prospect of industrialization of macro/nano materials. Starch is the most abundant and inexpensive biopolymer. With the drawbacks of poor strength, water resistibility, thermal stability and processability of pure starch, some biodegradable synthetic polymers such as poly (lactic acid), polyvinyl alcohol were composited to electrospinning. To the best of our knowledge, composite nanofibers of polyvinyl alcohol/starch from bubble electrospinning have never been investigated. In the present study, nanofibers of polyvinyl alcohol/starch were prepared from bubble electrospinning. The processability and the morphology were affected by the weight ratio of polyvinyl alcohol and starchy. The rheological studies were in agreement with the spinnability of the electrospinning solutions.