Electrospinning is an efficient technique for the fabrication of polymer nanofibers. The charges inside the polymer jet tend to repel each other so as to stretch and reduce the diameter of the polymer fibers. By rotating the collector at a fast angular speed, nanofibers with specific orientation can be obtained. In this study, nanofibers of Polyethylene oxide (PEO) with carbon black were prepared by electrospinning. PEO was dissolved in a mixture of water and ethanol. PEO is known as an electrolytic polymer. With the blending of carbon black powders, its electrical properties along the fiber direction were investigated. The fiber morphology and characteristics were studied by SEM and polarized FTIR.