Spectrophotometric, morphologic and dielectric properties of polyacrylonitrile (PAN) composite films in the presence of pyrrole derivatives were reported in this paper. The composite films were fabricated by oxidative polymerization of pyrrole (Py), N-methyl pyrrole (NMPy) and N-phenyl pyrrole (NPhPy) by cerium(IV) on polyacrylonitrile matrix. The effect of temperature on the dielectric properties was studied in the frequency range from 0.05 Hz up to 10 MHz and in the temperature range from 0 A degrees C up to 250 A degrees C. Conductivity was increased with temperature due to increase of the mobility of charge carriers in the composite films. By increasing the temperature, the dipoles become free and respond to the applied electric field in composite structure; thus, the polarization and dielectric constant increases. PNPhPy-PAN composite films exhibited the highest dielectric constant, AC conductivity and tan delta.