The oxidative polymerization of pyrrole (Py) by cerium(IV) on Poly(Acrylonitrile-co-Vinyl Acetate) matrix was performed. Nanofibers were obtained from this solution by the electrospinning method. A new absorption band was observed corresponding to the CH in plane vibration of polypyrrole (PPy) by Fourier transform infrared-attenuated total reflectance spectrophotometric analysis. A linear relationship was determined between the absorbance ratios of functional groups corresponding to the conjugated polymeric units and initial Py concentrations in the presence and absence of Py. Scanning electron microscope images indicated that the diameters of nanofibers were dependent on PPy content and that the average nanofiber diameters were reduced with increasing the initially added Py concentration. The alternating current conductivity of nanofibers was increased with frequency, particularly in the higher frequency region (> 10(5) Hz).