Electrospinning is a kind of method to produce nanofibers. The shape of electrospinning nanofibers is effected by different surface charge. In the process of electrospinning, if the spinning solution is absolutely insulating, or the applied voltage is not high enough, the electrostatic force will not be able to overcome the surface tension, so it can not produce nanofibers. However, if the spinning solution is added salt, the problem is solved. This article investigated the shape of nanofibers with different content of LiCl. The research shows that after adding different content of LiCl in PVA solution, the diameter, the length of stability and instability part of nanofiber are different. LiCl significantly reduce the surface tension of the PVA solution, so the sticky of the polymer is reduced and the process of spinning can be easy. In the same content of PVA solution, with the content of LiCl increase, the diameters of the nanofibers increase,the jet instability occur earlier and the stablility length of it decrease. 1. To stability part of jet, The sequence is that the power exponent of stability part is 0.5. 2. To instability part of jet, The sequence is that the power exponent of instability part is 0.25.