Chemical oxidative polymerization of N-Methyl Pyrrole (NMPy) by cerium(IV) on Poly(Acrylonitrile-co-Vinyl Acetate) matrix in N,N-dimethylformamide (DMF) was performed. Electrospinning technique was used for the preparation of P(AN-co-VAc) solutions with uniformly distributed Poly(N-Methyl Pyrrole) (PNMPy) nanoparticles. In the presence of PNMPy, a new absorption band appeared at 1312 cm(-1) which corresponds to CH in plane vibration peak. The dielectric properties of nanofiber composites were evaluated on the basis of the complex permittivity. The SEM and AFM images of composite nanofibers showed that the PNMPy nanoparticles with the dimensions of 20-40 nm were distributed homogeneously.