The combined use of two techniques namely electrospray and spinning is made use in a highly versatile technique called electrospinning, which produces the diameter of polymer fibers range from nanometer to sub-micron. In this work, we have studied effects of adding LiCl on the morphology and diameter of electrospun poly(ethylene oxide), and we have also evaluated systematically the effect of three important solution parameters on the morphology of electrospun poly(ethylene oxide): molecular weight, solution viscosity and electrical conductivity. We find that molecular weight is strongly correlated with the formation of bead defects in the fibers, the smaller molecular weight, the more beads defect density. As a result, the fibers have beads-in-string structures. Electrical conductivity increases, then decreases as molecular weight increases. Solution viscosity has been found to most strongly affect fiber size, with fibers diameter increasing with increasing solution viscosity according to a power law relationship. In addition, we find evidence that solution viscosity and electrical conductivity affect the interesting morphology of the electrospun nanofibers, and result in doubling and forming membrances phenomena.