In this study, poly(acrylonitrile-co-vinyl acetate) (P(AN-co-VAc)) composite films were prepared by chemical polymerization of pyrrole(Py), N-methyl pyrrole (NMPy) and N-phenyl pyrrole (NPhPy) with cerium(IV) [Ce(IV)] on P(AN-co-VAc) matrix. An increase was observed in the absorbances of CN ring stretching vibration (1451 cm(-1)) by introducing pyrrole (Py) derivatives on P(AN-co-VAc) matrix. The nitrile (CN) and carbonyl (C=O) groups played a significant role on the interactions with cationic sites of Py derivatives. Conductivity was increased in the presence of carbonyl (C=O) groups due to their additional negative charges on P(AN-co-VAc) matrix compared to PAN. Poly(N-Phenyl Pyrrole) (PNPhPy) exhibited higher dielectric constant and AC conductivity in the frequency range between the 10(-2)-10(7) Hz. The TGA results exhibited shifts of peak to higher temperatures by the presence of Py derivatives by increasing the weight loss %.