This research work has concern a development of novel semiconducting polymer based on chemically modified poly (vinyl chloride) (PVC) for uses as components in energy related devices. The primary aim of this work was to investigate the effect of electrospinning process on morphology and conductivity of the modified PVC. Chemical structure of PVC was firstly modified by reacting it with sodium hydroxide solution under different reaction time to obtain dehydrochlorinated PVC with a variety of degree of dehydrochlorination. Changes in chemical structure of the polymer was determined by FTIR technique. Degree of dehydrochlorination and chemical structural change was also confirmed by 1H-NMR technique. Morphology of the electruspun fibers were examined by SEM technique. Changes in conductivity of the polymers were also discussed in light of degree of dehydrochlorination and morphology of the materials.