The electrospinning process and morphology of electrospun nanofibers depend on many processing parameters. These parameters can be divided into three main groups: 1) solution properties; 2) processing conditions; and 3) ambient conditions. In this paper, we report the results of a comprehensive investigation of the effects of changing the conductivity of polyethylene oxide (PEO)/water solution on the electrospinning process and fiber morphology. The effects of the conductivity of PEO solution on the jet current and jet path are discussed. Furthermore, the fiber diameter and fiber uniformity are investigated by using scanning electron microscopy techniques.